Catalysts for demetallization treatment of hydrocarbons supported on sepiolite

ABSTRACT

This invention relates to a catalyst for hydrotreatment of hydrocarbons comprising one or more of metals selected from the group consisting of transition metals and metals of group IIb of the periodic table supported on sepiolite. More particularly it relates to a catalyst effective in the selective demetallization treatment of hydrocarbons.

This is a continuation, of application Ser. No. 748,752, filed Dec. 9,1976 and now abandoned.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

This invention relates to a catalyst for hydrogenation or selectivedemetallization treatment of hydrocarbons, which comprises one or moreof metals selected from the group consisting of transition metals andmetals of group IIb of the periodic table supported on sepiolite, andthe method for preparation of said catalyst as well as the process forthe hydrogenation and demetallization in the presence of said catalystunder a hydrogen pressure and at a high temperature.

(2) Description of the Prior Art

Impurities such as sulfur, nitrogen and metals are contained in thehydrocarbons including crude oils, heavy oils, cracked oils, deasphaltedoils, topped residual oils, vacuum gas oils, tar sands, bitumens, shaleoils, or the mixtures thereof. These impurities are discharged into theatmosphere together with the exhaust gas when these hydrocarbons aresubjected to combustion, becoming a source of the environmentalpollution. Also, the soluble metals contained in the hydrocarbons aredeposited on a catalyst in the catalytic treatment of hydrocarbons,causing a marked decrease in the catalytic activity of the catalyst andthe selectivity of the reaction. Therefore, in order to utilize thehydrocarbons as a harmless energy source or as the starting material ina catalytic process, it is necessary to remove sulfur, nitrogen andmetals from them beforehand. Above all, it is becoming an indispensablerequisite that the metals are removed previous to the treatment ofnon-metallic impurities such as sulfur and nitrogen. Since these metalswere, heretofore, simultaneously treated together with sulfur, nitrogenand the like without subjecting to any pretreatment, it was necessitatedto use the catalyst in an amount in large excess to the theoreticalamount required for desulfurization or denitridication. But as thecatalysts for these desulfurization and denitrification are veryexpensive the development of an inexpensive catalyst which is excellentin demetallization characteristic has been desired.

In the prior art, when demetallization treatment is carried outbeforehand, hydrocarbons are treated by utilizing either an ordinarydesulfurization catalyst or a waste catalyst having almost nodesulfurization activity, or using bauxite, red mud and the like as thecatalyst in the so-called guard reactor. All these catalysts, however,have defects in that the activity of demetallization is low or the lifetime of the catalysts is too short, and moreover, they are veryunsatisfactory for the purpose of carrying out a selective and effectivedemetallization reaction.

In the case of a catalyst having a relatively high demetallizationactivity, usually the desulfurization reaction also proceedssimultaneously, and as a result this often causes trouble in theutilization of the hydrocarbons thus demetallized. For example, red mudis available at a very low price and in quantities and is a usefulcatalyst for demetallization having the activity of removing, under ahigh hydrogen pressure, the metals contained in hydrocarbon oils,especially vanadium, nickel and iron. But, it has defects in that thedemetallization treatment must be carried at high temperatures requiringa very long contact time. The oils treated in the presence of the redmud-catalyst is extremely instabilized as a result of a long residencetime at a high temperature, and further it may happen that carbonaceoussubstances are caused to be deposited to clog the reactor near the exitof the catalyst layer. In order to avoid such trouble the treatment maybe carried out at a relatively low temperature, but it takes a stilllonger time and is very disadvantageous from an economical viewpointbecause of the necessity of providing .[.a large-sized reaction.]..Iadd.large-sized reactor .Iaddend..

Bauxite is also available at a price as low as that of red mud and has ademetallization activity higher than that of red mud. But bauxite hasdefects in that the lowering in the activity is considerably large onaccount of its small pore volume and the life time of catalyst is short.A catalyst having such a small pore volume as bauxite is not suitablefor the treatment of hydrocarbons containing a high content of metals.

Incidentally, the demetallization reaction of hydrocarbons is theso-called hydrogenation reaction which is carried out in the presence ofcatalyst under a hydrogen pressure and at a high temperature. It hasbeen known for a long time that the demetallization reaction takes placetogether with a desulfurization reaction since metals are deposited on acatalyst in the course of the desulfurization reaction. In thedesulfurization treatment using a conventional desulfurization catalyst,the higher the desulfurization ratio is raised, the higher thedemetallization becomes, and the desulfurization and demetallizationreactions take place in an almost definite proportion under the samecondition. On the contrary, even when demetallization is carried out byusing a conventional desulfurization catalyst, it is totally impossibleto avoid the desulfurization reaction which takes place in the definiteproportion. These phenomena will be further studied in comparison withthe effects obtained by the present invention in the following.

SUMMARY OF THE INVENTION

The present inventors have found that a catalyst which comprises one ormore of metals selected from the group consisting of transition metalsand metals of group IIb of the periodic table supported on sepiolitecarrier is an inexpensive catalyst which is very useful for thedemetallization reaction of hydrocarbons and by which thedemetallization reaction can be selectively carried out.

Accordingly, it is an object of the present invention to provide a novelcatalyst for hydrotreating of hydrocarbons. It is another object of theinvention to provide a method for preparation of the catalyst. It is afurther object of the invention to provide a method for desulfurization,denitrification and/or demetallization of hydrocarbons by using thecatalyst. Other objects and aspects of the present invention will becomeapparent from the following description.

These objects of the present invention have been fulfilled by theembodiments represented by: a novel catalyst for hydrotreating ofhydrocarbons which comprises an effective amount of one or more ofmetallic compounds supported on sepiolite carrier, the metal(s) of saidmetallic compound(s) being selected from the group consisting oftransition metals and metals of group IIb of the periodic table: amethod for preparation of the catalyst which comprises two combinedtreating steps: and a method for desulfurization, denitrification and/ordemetallization of hydrocarbons which comprises treating thehydrocarbons in the presence of pressurized hydrogen and at a hightemperature by using the catalyst.

When compared with a conventional desulfurization catalyst, the catalystof the present invention has a far much larger ratio of demetallizationrate to desulfurization rate and provides a more selectivedemetallization reaction. Thus, the catalyst is very valuable in theindustrial use as a novel catalyst for demetallization. Further, thepresent invention provides a catalyst having a high hydrogenationactivity and a longer life time for treatment of hydrocarbons insuitably chosen combinations of the steps of grinding, kneading,moisture conditioning, and/or molding, utilizing the unique propertiesof sepiolite.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a photomicrograph (magnification×10,000, with an electronmicroscope) of natural sepiolite of Spanish product which was groundinto a powder 50 mesh or smaller in size and subjected to moistureconditioning.

FIG. 2 is a photomicrograph (magnification×10,000) of theabove-mentioned moist sepiolite which was kneaded by passing through anextruder 3 times.

FIGS. 3 and 4 are the graphs showing the changes in the distribution ofspecific surface areas as well as those of pore volumes in the stages ofgrinding, kneading and molding of sepiolite according to the presentinvention, respectively.

FIG. 5 shows the changes in the results obtained by X-ray diffractiontests of the starting material sepiolite and the sepiolite which was notincorporated with additives and baked at 250° C., 450° C. or 650° C., ascompared to the result obtained by the test of the molded product(calcined at 500° C.) which was prepared according to the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

The catalytic metal or metals to be supported according to the presentinvention, are one or more of metals selected from the group consistingof metals of group IIb and transition metals of the periodic table.Namely, use is made of one or more of the metallic compounds selectedfrom the group consisting of the compounds of Cu, Ag and Au of group Ib;Sc, Y, lanthanides and actinides of group IIIa; Ti, Zr and Hf of groupIVa; V, Nb and Ta of group Va; .[.Cu.]. .Iadd.Cr.Iaddend., Mo and W ofgroup VIa; Mn, Tc and Re of group VIIa; and Fe, Co and Ni of iron group,Ru, Rh and Pd of palladium group, Os, Ir and Pt of platinum group; andZn, Cd and Hg of group IIb. Among these metals the preferable are Co,Ni, Fe, Cu, lanthanides, V, Cr, Mo and W. Furthermore, the combined useof both one or more compounds of the metal(s) selected from Co, Ni, Fe,Cu, and lanthanides, and one or more compounds of the metal(s) selectedfrom Mo, W and V is especially effective in the present invention.

These metals are generally utilized in the forms of nitrates, sulfates,salts of metallic acids, complex salts or other water-soluble compounds.The addition of these compounds to sepiolite can be conducted accordingto the conventional methods such as immersion, spraying and kneading.These compounds are employed generally in an amount of 0.1 to 20% byweight (as metal) on the basis of carrier (as anhydride), and usually0.2 to 10% by weight will suffice.

Sepiolite is a porous magnesium-silicate mineral which is also calledmeerschaum. The sepiolite naturally occurs as a secondary mineral in aserpentine; and its synthetic product was prepared from cheaplyavailable silicic compounds and magnesium salts in 1935 or so and is nowmarketed under the trade name of "magnesiumtrisilicate". For the purposeof the present invention, any natural or synthetic sepiolite can beemployed, and both the α-type sepiolite and β-type sepiolite that areknown to exist can be used in the present invention. When sepiolite isused as the carrier of catalyst, the starting material sepiolite isemployed as it is or the sepiolite is dried below 200° C. or usually atabout 100° to about 120° C. to remove the adhered moisture, and groundto the desired particle size. In general, the sepiolite having aparticle size of 0.3 to 3 mm in volume average diameter is most oftenemployed. If necessary, sepiolite can be treated in combined steps ofgrinding, molding, sintering, etc. so as to meet the particular usepurpose. The size and shape of the carrier can be suitably selected inaccordance with the reaction conditions of hydrotreating, the types ofthe reaction apparatus and the like.

In the case of some metals, the ion-exchange property of sepiolite canbe utilized to have the metals supported on sepiolite. These metalsinclude those of Groups Ib, IIb and IIIa and iron group of the periodictable and preferably Co, Ni, Fe, Zn, Cu and lanthanides. By contactingan acidic aqueous solution of these metal ions with sepiolite, magnesiumcontained in the sepiolite is ion-exchanged with these metals to havethese metals supported on the sepiolite. These metals are used in theform of an aqueous solution of the salts of mineral acids such aschlorides, sulfates and nitrates and/or the salts of organic acids suchas formates and acetates. If necessary, inorganic acids or organic acidsare added to the solution so as to adjust the pH of the solution to 1-7.

The concentration of the metallic salt(s) in the aqueous solution isdetermined according to the amount of the metal(s) to be supported, thekind thereof and the condition of the supporting treatment. When aconcentrated solution is employed, magnesium contained in sepiolitetends to elute from the sepiolite in larger amounts relative to theamount of the metal to be supported. Therefore, in the case where toohigh a concentration is employed, the structure of sepiolite may bedestroyed until it eventually pulverizes. A similar phenomenon may takeplace when an inorganic acid or an organic acid is added to the solutionin an extremely large amount. Therefore, it is necessary to employ theacidic solution having a pH in the range of 1 to 7 as above described. Asolution having a pH lower than 1 may also be used, but in this case thetreatment should be conducted in a very short period of time. Theprocess of this invention is characterized by that the metal issupported on the carrier while portion of the magnesium contained in thesepiolite is being allowed to dissolve, as already described.Accordingly, it is presumed that the metal is ion-exchanged with aconsiderable amount of the magnesium to be supported on the sepiolite.The metal thus supported does not dissolve even when rinsed with purewater, but dissolves in an acidic solution. In the process of thisinvention it is essential that the metal supported is substituted formagnesium, and thus the metal simply deposited on the sepiolite withoutbeing substituted is lower in the catalytic activity per unit weight ofthe metal than that of the metal substituted. Therefore, it is desirablethat the metal simply deposited on the sepiolite is removed by rinsingand effectively reused.

The sepiolite thus treated to support the metal and rinsed can be usedas it is, or after drying or baking at a temperature below about 1,000°C., or after grinding and molding into the desired shape.

When both the metal(s) which can be supported according to theion-exchange method and the metal(s) which can not be supported therebyare to be supported on the same sepiolite, the conventional impregnatingmethod, spraying method and the like can be applied using an aqueoussolution containing both the metals; but, it is very effective for theactivity of the resulting catalyst to support the former metal(s) by theion-exchange method and then to support the latter metal(s) as anaqueous ammonia or amine solution thereof. In the process of thisinvention it is also essential that the supporting treatment is carriedout by an ion-exchange reaction using an acidic aqueous solution in thefirst step, and using an basic aqueous solution in the second step, andmoreover, the first and second steps are carried out in this order.

Usually, the metal supported in the first step is not the same as themetal supported in the second step, but if desired, the same metal canbe supported in these two steps. In the first step, the magnesiumcontained in sepiolite is substituted by the metal dissolved in anacidic aqueous solution through an ion-exchange reaction, while in thesecond step, the supporting is per se the same as that achieved by theconventional impregnating method. Therefore, it is considered that themetal in the first step is supported in a state quite different from themetal in the second step. These states of the metals supported can notbe distinguished from each other according to the ordinary analysis orby an observation of the microstructure. But, as a clear difference isfound in the catalytic activity, after metals have been supportedbetween the catalyst prepared by these two-step method and the catalystobtained by the conventional one-stage method, it is judged that each ofthe metals treated according to the two-step method of the presentinvention is supported in a structurally different state from the metalstreated by the conventional one-stage method, and thus, this results inthe difference in catalytic activity.

The kind and amount of the metal(s) to be supported in the first stepare generally determined in accordance with those of the metal(s) to besupported in the second step, but as the amount of the metal to besupported in the first step 0.1 to 5% (as metallic element) by weightwill suffice.

In general, the sepiolite treated in the first step is rinsed with purewater and/or an aqueous solution containing ammonia or an amine andthen, if necessary, dried or baked at a temperature below 1,000° C.,followed by the treatment in the second step. In the above case it isessential that the metals supported in the first step are substituted bymagnesium, and since the catalytic activity per unit weight of themetals simply adhered on the sepiolite without being substituted islower than that of the metals substituted, the excess of these metals isremoved by rinsing and effectively reused. The sepiolite treated in thefirst step and then rinsed is usually as such, or after drying below1,000° C., subjected to the second step, but alternatively, it may alsobe ground and molded to the desired shape before subjecting to thesecond step.

The second step comprises supporting on a carrier one or more metalsselected from the group consisting of metals of Groups Va and VIa, andiron group of the periodic table and Cu, preferably from the groupconsisting of Mo, W, V, Ni, Co, Cu and the like, by impregnating saidcarrier with an aqueous ammonia and/or amine solution containing thesemetals. This step is substantially the same as the conventional methodfor supporting a catalytic metal on a carrier. As these metalliccompounds use is made of ammonium paramolybdate, ammoniumsilicotungstate, ammonium paratungstate, ammonium, vanadate, orchlorides, sulfates, nitrates or formates of Ni, Co, Cu, and the like.Of course, other prior known compounds which are stable or can beconverted to soluble compounds in a basic aqueous solution can also beused. These compounds are used by dissolving them homogeneously in anaqueous ammonia solution or an aqueous amine solution. The concentrationof these metallic compounds as well as of ammonia or amines in the basicaqueous solution can be determined according to the amount of the metalto be supported and the properties of the sepiolite carrier treated inthe first step. The metal to be supported in the second step can betreated in one-stage or multistage process. As the amount of metal to besupported in the second step generally 20% or less (as metallic element)by weight will suffice, but is preferably 2 to 20% by weight in thegroup of Mo, W and V and 0.1 to 10% by weight in Ni, Co and Cu. Thesepiolite carrying metallic compounds is baked or sintered at atemperature of 300° to 1,000° C., preferably 350° to 800° C. for use,but before use, it may also be pretreated, if necessary, such as bysubjecting to sulfidizing, etc. as it is in an impregnated state withoutbeing baked or sintered.

The sepiolite used as the catalytic carrier in the present invention isa porous substance which not only occurs naturally as a hydrousmagnesium silicate but also is readily available as a synthetic product,and is widely used as a catalytic carrier as well as an adsorbent andthe like. The natural sepiolite, however, is not constant in theproperties such as composition, pore volume, specific surface area, poredistribution and crushing strength. Further, when it is wanted to obtainthis material of a given particle size by crushing and sieving of itsmineral the yield is very poor. These defects have been a hindrance whenused industrially in quantities.

Although sepiolite itself is a very porous substance having a large porevolume, it is not only difficult to obtain the material of uniformquality, but also most of the material, as it is, is now always soporous as to be sufficient for specific purposes. Moreover, the poredistribution of natural sepiolite covers a very broad range. The presentinventors have found that the properties of the volume of large poresmore than 600 A in diameter occupying in the whole pore volume oftenaccounts for 35% or more. The larger the proportion of such large pores,the smaller the specific surface area as well as the crushing strengthof crushed product. Therefore, in some cases, where it is used ascatalytic carrier, such crushed sepiolite as it is, is undesirable inpractice for specific purposes.

The present inventors investigated the properties of the sepiolitesproduced naturally in various countries as well as their usefulapplication, and as a result found that sepiolite is a mineral havingvery unique properties and can be made into a molded product havingexcellent properties by subjecting it to specific treatment. Thus, theinventors have further succeeded in obtaining an excellent catalyst bymodifying the sepiolite used as catalytic carrier. The porous moldedproduct prepared according to the present invention has the followingcharacteristics:

(a) sepiolite having markedly large pore volume and specific surfacearea in comparison with those of the raw sepiolite can be readilyobtained;

(b) sepiolite having a larger specific surface area can be obtained bymaking the size of the pore volume comparable to, or smaller than thatof the raw sepiolite;

(c) the molded sepiolite has a sharp pore distribution; and

(d) the molded-sepiolite has a large crushing strength.

The relation between the pore volume and the specific surface area ofthe molded product obtained according to the present invention is notnecessarily critical, but it is possible to prepare the molded producthaving the desired pore volume and specific surface area.

It has been recognized by the present inventors that the porous moldedproduct having the above-described excellent properties obtainedaccording to the present invention is much improved in the fundamentalstructure of sepiolite in that the molded product is clearly differentfrom the raw sepiolite in both the physical and chemical properties fromthe physical and chemical studies such as composition analysis, X-raydiffraction, measurement of specific surface area, measurement of poredistribution, observation under an electron microscope, measurement ofcrushing strength and the like of the raw sepiolite, the intermediateproduct and the final product.

Since the above-mentioned change in fundamental structure is scarcelyobserved in the molding step of the ordinary porous powder materials, itis considered that such a change is peculiar to sepiolite and has anexcellent effect on the catalyst of the present invention.

Now the molding of sepiolite will be explained in the order of theprocedure. Natural or synthetic sepiolite as raw material is ground by agrinder. The particle size of the resulting sepiolite powder may be insuch a range as not to cause difficulty in the kneading or moldingprocess and is generally desirable to be smaller than 50 mesh. However,in order to carry out the kneading efficiency, it is preferable to makethe particle size as fine as possible. Accordingly, sepiolite isgenerally ground to fine powder in which 100-mesh or finer powderaccounts for 50% or more. The method for grinding is not especiallyrestricted, and either a wet method or a dry method can be employed.

The ground sepiolite is then treated in the following kneading step. Oneof the main characteristics in the process of the present inventionresides in that the ground sepiolite is subjected to moistureconditioning and then to sufficient kneading or mastication. In themoisture conditioning step prior to the kneading, water is added to theground sepiolite so as to carry out the kneading effectively and thefollowing molding efficiently and smoothly.

The final water content of the resulting moist sepiolite has largeeffects on the properties of the resulting catalyst and on the moldingproperties as well. The water content, therefore, is determined inconsideration of the properties of the raw sepiolite, the amount andkind of the additives later described, the properties of the kneadedmaterial, the method of molding, the intended use of the resultingcatalyst, and the like. In general, the water content of the sepioliteis adjusted to from 20 to 350% by weight on the basis of anhydroussepiolite, preferably to from 50 to 280% by weight. When the watercontent is less than 20%, it is difficult to obtain the catalyst havingthe desired properties as well as to mold it according to the ordinarymolding method. When the water content is more than 350%, the sufficientcrushing strength of the resulting catalyst can not be obtained and suchwater content is not practicable. In the case where additives are usedin combination, the above-mentioned range of water content can beapplied to the amount of a mixture of sepiolite and the additives. Whenthe moist sepiolite is molded by an extruder, its water content isgenerally in the range of 80 to 350% by weight, and when it is molded bya tableting machine, its water content is generally in the range of 20to 100% by weight.

The above-mentioned range of water content is characterized by beingvery large in comparison with those in the case where alumina,alumina-silica and the like are used as raw materials. This is due tothe structure of sepiolite, and such a large amount of water actseffectively in the kneading step. In general, the kneading of porouspowder is conducted to effect uniform dispersion of moisture andhomogenizing of the components of the mixture. In the case of thekneading of moist powder in the molding of porous powder such asalumina, alumina-silica, etc., it is known that the specific surfacearea and pore volume of the kneaded material gradually decrease as thekneading proceeds. Therefore, it has been the technical common sensethat the kneading is suppressed to such a minimum degree as required forenhancing the molding properties or crushing strength. Unexpectedly, inthe case of sepiolite, the more sepiolite is kneaded, the larger thepore volume and pore surface area become and the sharper the poredistribution becomes.

In order to clarify these unique properties, sepiolite was observedunder an electron microscope (magnification×10,000) to reach thefollowing conclusion.

Referring now to the drawings, the photomicrograph(magnification×10,000) of the sepiolite simply ground to fine powderindicates that the sepiolite fibers stick to one another to form thickfascicular fibers or lumps as clearly shown in FIG. 1. Whereas, thephotomicrograph of the sepiolite which was subjected to grinding andmoisture conditioning followed by sufficient kneading indicates that thethick fascicles and lumps of sepiolite fibers almost disappear, andshort and thin fibers are scattered in disorder, as shown in FIG. 2.Accordingly, when the molded sepiolite having such a structure as shownin FIG. 1 is compared with the one having such a structure as in FIG. 2,it will be readily understood that the specific surface area and porevolume of the latter are markedly increased in comparison with those ofthe former.

This phenomenon can also be proved by the changes in the distribution ofspecific surface area as shown in FIG. 3 as well as in the distributionof pore volumes as shown in FIG. 4 in each step of grinding, kneadingand molding of sepiolite which were treated in this order. It is shownin FIG. 3 that the specific surface area of the kneaded material (3) orthe molded material (4) is markedly increased in comparison with that ofthe sepiolite ore (1) of the ground sepiolite (2), and further thesurface area of the pores 600 A or smaller in diameter is markedlyincreased in the step of kneading although the surface area of the poreslarger than 600 A diameter does not make a large difference by thekneading treatment. In FIG. 4, it is also shown that the pore volume ofthe kneaded material (3), especially of the pores 600 A or smaller indiameter, is increased. In addition, in each of the data shown in FIGS.3 and 4, no additive was contained in (1) and (2), but (3) and (4)contained 10% (as alumina) by weight of alumina sol on the basis of drysepiolite.

The above-mentioned kneading can be carried out by an ordinary kneader,roll mill or molding machine such as an extruder, and may be done by anyother means which can untie the sepiolite fibers to separate fibers inthe presence of water. The purpose of the kneading is to increase thespecific surface area and the pore volume of the sepiolite to betreated, and the method and period of time for the kneading can bedetermined according to the properties of the resulting molded product,the properties of the raw material, the presence or absence ofadditives, the properties of the moist material, the type of thekneader, and the like. Incidentally, the kneaded material can be againsubjected to moisture conditioning, if necessary, to adjust the watercontent thereof to a suitable molding condition.

The sepiolite material which was subjected to kneading and moistureconditioning is air-dried and/or baked at a temperature below 1,000° C.The moist sepiolite material can be subjected to the air-drying and/orbaking in the form of mass or after molding it by conventional molderssuch as extruders and tableting machines. The massive material which wasair-dried and/or baked can be ground to a desired particle size to usein a slurry or paste form. The shape and size of the resulting catalystis determined according to the purposes of use and process. The crushingstrength of the resulting catalyst can also be controlled to meet thecondition of use by selecting a suitable method for preparation and asuitable temperature of drying and baking.

The present inventors found that the properties of the molded sepiolitecan be further improved by incorporating the following additives in thesepiolite material in the course of molding.

Mainly for the purpose of enhancing the crushing strength of theresulting catalyst, one or more additives selected from the followingadditives can be added to sepiolite:

(a) aluminium hydroxide sol, alumina silica sol, silica sol, otheraluminium-containing subtance, and other silica-containing substance;

(b) bauxite, kaoline, montmorillonite, allophane, bentonite,attapulgite, and other clay minerals; and

(c) higher alcohols, esters, ethers, urea, starch, sucrose and organicmolding auxiliaries.

These additives are employed to enhance the crushing strength of theresulting catalyst and may also be incorporated as a filler. Some ofthese additives may have a good effect on the properties and activity ofthe resulting catalyst when a suitable condition of preparing thecatalyst is selected. In general, the compounds of the above-mentionedgroup (a) give sepiolite some thermal stability and the compounds of theabove-mentioned group (c) can smooth the operation of kneading andmolding.

As for the amounts of the additives to be added for these purposes, thecompounds of the group (a) are generally added in an amount of 0.5 to90% (as anhydrous oxide) by weight, preferably 1 to 80% by weight andmost preferably 1 to 20% by weight. The compounds of the group (c) aregenerally added in an amount of 1 to 30% by weight. The kind and amountto be added of these additives can be determined in consideration of thepurpose of employing the resulting catalyst, and these additives may beadded to sepiolite in a large excess if so required. The additivesselected from each of the groups (a), (b) and (c) can be used incombination to enhance the various effects on the resulting catalyst.These additives are generally added to sepiolite in the course ofkneading in the form of ground powder or paste, and may be admixed tosepiolite prior to supporting metals such as Co and Ni on sepiolite.

Besides these additives, to the sepiolite mixture may be added thecompounds which were to be employed in the pre-treatment of sepiolite(which is a preferred treatment of sepiolite and is explained below indetail) such as inorganic acids, organic acids, metallic acids, ammoniumsalts thereof, salts of ammonia derivatives, or magnesium salts. Ofcourse, it is not necessary to add the compounds when the compoundsemployed in the pre-treatment remain in the sepiolite material.

The common effect obtained by addition of these additives is that a veryexcellent thermal stability is exhibited when molded materialscontaining the additives are subjected to calcining or sintering, incomparison with the case where no additives are added. This effect isconcretely indicated by an increase in strength, an increase in porevolume and the like, but most distinctly exhibited by the X-raydiffraction of the sintered product from the viewpoint of its structure.As shown in the graph of FIG. 5, the results of X-ray diffraction of theraw sepiolite (1) air-dried at room temperature and the sepiolite (2)dried at a relatively low temperature of 250° C. indicate substantiallythe same patterns. While, in the X-ray diffraction of the sepiolite (3)or (4) calcined at 450° C. or 650° C., a peak in the neighborhood of20=7° disappears and the changes in other small peaks are observed. Inthe case of the molded product (5) which was prepared by adding theadditives to the same sepiolite and calcining at 500° C., the peak inthe neighborhood of 20= 7° does not disappear remaining as it is andother small peaks are more similar to those of (1) and (2) than (3) and(4). From these results, it is clear that the additives have someeffects on the thermal stability of sepiolite.

The effects of some of the additives on the molded products are moreconcretely explained as to each group of the additives in the following.

The additives shown in the groups (a) and (b) serve to enhance thecrushing strength of the molded products, without substantiallydecreasing the pore volume. Especially, aluminium salts of the group (a)serve to markedly decrease the large pores 400 A or more in diameter inthe pore distribution and to increase the pore volume within the rangeof pores 400 A or less in diameter. Furthermore, the addition of thealuminium salts results in the marked enhancement of crushing strengthof the resulting molded product, even in a very small amount. Thepresence or formation of acids in the sepiolite mixture results in theespecially sharp distribution of pores. Such sharp distribution is alsoobtained by addition of the metal salts. These additives can be added tosepiolite in the course of grinding, moisture conditioning or kneading,alone or together with the additives of the other group shown above.

In the preparation of the catalyst using a sepiolite carrier forhydrotreating according to the present invention, the followingpretreatment step can be employed to enhance the catalytic propertiesand to improve the method for preparation of the catalyst.

A small amount of impurities such as calcium carbonate, magnesiumcarbonate and magnesium-calcium carbonate may be contained in thesepiolite generally employed. Although some of these impurities areremoved in the course of the metal-supporting step using an acidicaqueous solution, the remaining impurities may have an adverse effect onthe activities of the resulting catalyst, especially on thehydrogenation activities thereof such as those of desulfurization anddenitrification. Further, the presence of these impurities results indecrease in the crushing strength of the resulting catalyst since someof the impurities are dissolved in the course of the metal-supportingstep. Also, a further complicated treatment is required to recover thewaste liquid in which these impurities were dissolved, in themetal-supporting step.

The pretreatment step employed in the present invention hassubstantially eliminated the above-mentioned defects.

In the pretreatment step, is employed an aqueous solution containing oneor more of the compounds selected from magnesium salts, inorganic acidssuch as mineral acids and carbonic acid, organic acids, ammonium saltsand salts of ammonia derivatives. Incidentally, the mineral acidsinclude nitric acid sulfuric acid, hydrochloric acid, phosphoric acidand the like. The organic acids include formic acid, oxalic acid, aceticacid, tartaric acid and the like. Carbonic acid is usually employed inthe form of an aqueous solution in which carbon dioxide was dissolvedunder normal or higher pressure. The ammonium salts include ammoniumnitrate, ammonium sulfate, ammonium phosphate, ammonium carbonate,ammonium oxalate, ammonium acetate, ammonium tartarate, and the like.The salts of ammonia derivatives include trimethylamine hydrochloride,aniline hydrochloride and the like.

The composition and concentration of these treating liquids are notespecially restricted. It is generally effective to employ a solutionhaving a pH in the range of 1 to 7, but an acidic solution of lower thanpH 1 may be used at a low temperature and with a short-time treatment.

The pretreatment is not especially restricted as to the temperature andtime of the treatment, and is generally carried out at a temperaturebelow 100° C. and for more than several minutes. The pretreatment may beperformed in a shorter time depending on the properties of sepiolite tobe treated.

In the course of the pretreatment, magnesium elutes in the treatingsolution, and the amount of the magnesium eluted depends on the treatingcondition of sepiolite. In general, the lower the pH of the treatingsolution is; the longer the treating time is, or the higher the treatingtemperature is, the larger the amount of magnesium to be eluted becomes.

The present inventors have found that magnesium to be eluted comes fromthe magnesium hydroxide, magnesium carbonate and dolomite componentswhich are present as impurities in sepiolite, by observing the state ofsepiolite before and after the pretreatment was effected. Thus, thepresent inventors have got information that one of the reasons that thepretreatment has good effect on the subsequent metal-supporting step isdue to the elution of most of the impurities from sepiolite.

The present inventors have further found that the properties of theresulting sepiolite catalyst, such as physical property, activity,reaction selectivity and lifetime, depend largely on the preparationprocess such as method of supporting metals, method of pretreatingsepiolite and method of molding.

A method for preparation of the catalyst based on the effectivecombination of the above-mentioned steps is illustrated in thefollowing.

In case that a metal or metals such as Co and Ni are supported onsepiolite by way of ion-exchange reaction, the pore volume and specificsurface area of the sepiolite are decreased owing to a phenomenon whichhas not yet been solved but is presumed to be due to electrostaticintermolecular force. Accordingly, the overall performance of thecatalyst for hydrotreating hydrocarbons is not satisfactorily exhibited,although the activity of catalytic metal is increased by employing theion-exchange method.

A metal on sepiolite-catalyst which is satisfied with the requirementsfor pore volume and specific surface area and contains the supportedmetal or metals exhibiting an excellent catalytic activity, can beobtained by the following procedure. Before having a metal or metalssupported on sepiolite, water is added to sepiolite. The mixture issubjected to a sufficient kneading or mastification to obtain a carriermaterial having such pore volume and specific surface area as aredesirable for a catalytic carrier, followed by adjusting the watercontent thereof. The sepiolite thus treated is, as it is or aftermolding, subjected to drying, baking or calcining to fix the desiredpore volume and specific surface area obtained by the kneading. Theresulting sepiolite is treated with an acidic solution containing ametal or metals such as Co and Ni according to the ion-exchange method,to have the metal supported thereon.

The method for preparation of the present catalyst comprises the step ofkneading or calcining and the subsequent step of supporting one or moremetals, although these two steps can also be carried out in the reverseorder.

In this method, it is essential that the baking or calcination should becarried out at a temperature of lower than about 400° C. When thecalcination is carried out at a temperature of higher than about 400°C., some changes will be brought about in a part of sepiolite owing tofusion and the like and the amount of the catalytic metal such as Co andNi, supported according to the ion-exchange method, may be decreased.

It is to be noted that the pore volume contracts in the course of themetal-supporting step. The present inventors have found that thisphenomenon of contraction takes place in a relatively low degree in thepores smaller than several hundreds A in diameter, but is markedlyexhibited in the pores in the range of several hundreds to severalthousands. A in diameter.

Therefore, by utilizing such phenomena advantageously, an excellentcatalyst having high activity can be prepared in accordance with thepurpose of catalyst and the properties of hydrocarbons to be treated.

For example, a catalyst having a high ratio of large pores severalhundreds to several thousands A in diameter possesses a large porevolume but a small packing density; accordingly, the specific surfacearea per packing volume becomes smaller. In accordance with researchesmade by the present inventors, such catalyst possesses a longerlifetime, especially in hydrotreating heavy oils, since clogging ofpores owing to deposition of metals and the like is much reduced, butits activity is lowered; therefore, it is necessary to make the ratio oflarge pores as small as possible by controlling the pore volume to sucha suitable extent that clogging of pores can be regulated.

When a heavy oil having a large metal content as much as 500 ppm to1,000 ppm is treated mainly for the purpose of demetallization, it isdesirable to employ a catalyst having a high ratio of large pores. Butin case of hydrotreating a usual heavy oil containing metals as much asseveral hundreds ppm, a treated oil containing very small amounts ofmetal and sulfur can be obtained by using a catalyst with higheractivity in which the ratio of large pores is reduced.

When it is intended to prepare a catalyst having a relatively high ratioof large pores for treating heavy oils containing a very large amount ofmetals, such catalyst can be obtained by selecting the conditions ofkneading and moisture conditioning in such a way as to spread the poredistribution towards larger pores, although some of the large pores maybe eliminated by means of the treatment with acids or ammonium salts, orthe metal (Co, Ni, etc.)-supporting treatment.

Alternatively, the above-mentioned method can be carried out in thereverse order, that is, in the order of the metal-supporting step andthe subsequent kneading, molding and/or baking (or calcination) step.According to this method, a metal on sepiolite-material is incorporatedwith water, the resultant mixture is subjected to kneading ormastification, and then the water content thereof is adjusted, ifdesired followed by molding; whereby it is possible to recover the porevolume and specific surface area which were reduced in the course ofion-exchange treatment. Thus, a catalyst having a large pore volume andspecific surface area can be obtained. A catalyst having a larger porevolume and specific surface area can be obtained by selecting suitableconditions of these treatments. When calcination or sintering is carriedout after kneading or molding step in the process, it can be effected ata temperature of lower than about 1,000° C.

As described above, by treating sepiolite in accordance with thesuitable and selected combination of the metal-supporting, kneading,molding, calcination and/or pretreatment, can be obtained a catalystwhich is very effective for hydrotreating hydrocarbons and especiallyfor demetallization, desulfurization and denitrification.

In addition, a catalyst having an excellent demetallization activity canbe obtained by simply mixing the catalyst of the present invention witha used catalyst containing one or more metallic compounds of which metalor metals are selected from the transition metals and the IIb groupmetals of the periodic table. In this case, if so desired, the usedcatalyst may be ground and sepiolite may be subjected to grinding,moisture conditioning, molding or the pretreatment.

Of course, the metal on sepiolite-catalyst of the present invention hasan excellent demetallization activity. A demetallization activity can beexhibited by employing a mixture of the catalyst of the presentinvention and a conventional catalyst for hydrogenation, or the catalystcomprising metal or metals supported on a mixture of sepiolite and aconventional carrier material. In case of adding sepiolite to aconventional carrier material and mixing them to provide the resultingcatalyst with demetallization activity, the amount of sepiolite in themixture is generally more than about 5% by weight for enhancing thedemetallization activity of the resulting catalyst to some extent, andmore than about 20% by weight for obtaining an excellent demetallizationactivity. Therefore, it is to be noted that a catalyst comprising themetal or metals supported on a mixture of sepiolite and the othercarrier material is also included in the scope of the present invention.

Incidentally, it is to be noted that as a result of concomitantlyemploying sepiolite and other conventional carrier material as describedabove, the activity and lifetime of the resulting catalyst are enhancedas well as the cost of carrier is lowered in comparison with those ofthe conventional carrier, since sepiolite has a large pore volume and isavailable at a lower price than some of the conventional carriermaterials.

The catalyst of the present invention can be employed in a very widevariety of hydrotreating reaction and for a very wide range ofhydrocarbons. The catalyst is very useful for desulfurization,denitrification and hydrogenation of light oils such as gasoline andkerosene, and also for demetallization, deasphaltening, desulfurization,denitrification, hydrogenation and hydrocracking of heavy oils such asvacuum gas oils, tar sands and bitumens.

Since the catalyst of the present invention is effective for varioushydrotreating methods and a very wide range of hydrocarbons, a broadrange of reaction conditions can be employed. But, the partial pressureof hydrogen is generally in the range of about 10 to about 350atmospheric pressure and preferably about 15 to 300 atmosphericpressure, and the reaction temperature is generally in the range ofabout 200° to about 470° C. and preferably about 200° C. to about 450°C. These reaction conditions can be optionally selected according to theproperties of hydrocarbons, the purpose of hydrotreating, the method ofreaction and the like. In the same way, a conventional method ofreaction can be employed in the present invention. For example, aconventional flow-type fixed bed, moving bed or fluidized bed reactorcan be advantageously employed.

The metal on sepiolite-catalyst of the present invention ischaracterized in that the demetallization ratio is selectively enhancedby hydrotreating hydrocarbons under the condition of high partialpressure of hydrogen sulfide. When hydrocarbons are hydrotreated in thepresence of a conventional catalyst for desulfurization, it is knownthat in the atmosphere of high partial pressure of hydrogen sulfide, thecatalyst is poisoned by hydrogen sulfide to gradually decrease thedesulfurization activity of the catalyst. It is also known thatdemetallization ratio is accordingly lowered as the desulfurizationactivity is lowered. Contrary to the conventional technical knowledge,the demetallization activity of the metal on sepiolite-catalyst ismarkedly enhanced as the treating time elapses in the reaction systemsubstantially containing pressure of hydrogen sulfide, although itsdesulfurization ratio is gradually lowered. Accordingly, the proportionof demetallization ratio to desulfurization ratio becomes graduallylarger as the reaction time passes, and as a result a selectivedemetallization reaction takes place. In this case, the reaction iseffectively carried out under .Iadd.a .Iaddend.partial hydrogen.Iadd.sulfide .Iaddend.pressure of more than about 10 kg/cm² andpreferably more than about 30 kg/cm² .

By utilizing such unique properties of the metal on sepiolite-catalystof the present invention, an efficient desulfurization process can becarried out combining two reaction steps, one being under high partialpressure of hydrogen sulfide and the other being under rather lowpartial pressure thereof.

The reaction process comprises the first step in which a selectivedemetallization of hydrocarbon is carried out under high partialpressure of hydrogen sulfide followed by removing hydrogen sulfide gasdissolved in the hydrocarbons thus treated and the subsequent secondstep in which desulfurization of the resulting hydrocarbons is carriedout under rather low partial pressure of hydrogen sulfide. Thus, in thesecond step, a rapid decrease in catalyst activity owing to depositionof metal on the catalyst is avoided, and the activities of the catalystcan be advantageously and fully utilized. Incidentially, the hydrogensulfide gas which was generated in the second step can be recoveredtogether with hydrogen gas and recycled to the first step for reuse. Thehydrotreating conditions in the first and second steps are determinedaccording to the kind of the hydrocarbon to be treated. The sameconditions may be applied to the both steps, and the reactions aregenerally carried out under hydrogen pressure of about 10 to about 350kg/cm² and at a temperature of about 300° to about 500° C.

The present invention will be further explained by way of the followingexamples. The percentage (%) and ratio (ppm) employed in the examplesare based on weight unless otherwise specified.

EXAMPLES 1-18

A sepielite carrier was obtained by drying a sepiolite mineral ofSpanish product at 120° C. for 2 hours and regulating the particle sizethereof within the range of 20 to 6 mesh of US Standard Sieve. Thecarrier had a specific surface area of 82 cm² /g and a pore volume of0.57 cc/g (the carrier dried at 200° C. was measured according tomercury porosimeter method). The sepiolite carrier was impregnated in anaqueous solution of nitrate or chloride of the catalytic metals shown inthe following Table 1 (for example, aqueous solutions of ammoniumvanadate, ammonium paramolybrate and sodium silicotungstate forvanadium, molybdenum and tungsten, respectively), by means of aconventional impregnating method to have the metal supported on thecarrier, followed by calcining at 500° C. to obtain a catalyst. When twoor more metals were to be supported on the carrier, a multistageimpregnating method was employed with one stage for each metal.

By employing each of these catalysts, a topped residual oil containing150 ppm of vanadium, 41 ppm of nickel, 3 ppm of iron and 2.87% of sulfurwas subjected to hydrotreating by using a high pressure flow-typereactor, under hydrogen pressure of 140 kg/cm² at a reaction temperatureof 415° C. and a liquid space velocity of 1.0 Hr⁻¹ with upward flow. Thedevanadiuming (removal of vanadium) ratio (DVR), desulfurization ratio(DSR) and the like, 50 hours after starting the reaction were measuredto determine the reaction activities of the catalysts. The results areshown in Table 1.

                  TABLE 1                                                         ______________________________________                                                                          Catalytic                                   Ex.                 Catalytic Metal                                                                             activity                                    Nos.   kind         amount of metal                                                                             DVR   DSR                                   ______________________________________                                        1      no           0             7%    1%                                           additive                                                               2      Cu           0.7           69    18                                    3      Co           1.3           73    20                                    4      Ni           3.0           75    24                                    5      Mo           2.0           54    21                                    6      W            2.0           44    15                                    7      V            2.0           37    10                                    8      Sm           1.9           75    17                                    9      Dy           2.3           73    17                                    10     Zn           2.7           52    11                                    11     Zr           1.2           58    13                                    12     Mo           1.1           40    15                                    13     Cu + Mo      Cu:1.2.Ne:3.1 82    32                                    14     Co + Mo      Co:0.8.Mo:2.7 88.sup.(1×2)                                                                  47                                    15     Cu + Ni      Cu:0.7.Ni:1.5 77.sup.(1×3)                                                                  24                                    16     Zn + V       Zn:2.5.V:10.3 79    46                                    17     Cu + Mn      Cu:5.0.Mn:4.2 81    23                                    18     Dy + Ni + Mo Dy:2.3.Ni:0.5.                                                                              90.sup.(1×4)                                                                  61                                                        Mo:3.0                                                    .sup.(1)                                                                              deironing (removal of iron) ratio                                                                 83-67%                                            .sup.(2)                                                                              denickeling (removal of nickel)                                               ratio               61%                                               .sup.(3)                                                                              denickeling (removal of nickel)                                               ratio               66%                                               .sup.(4)                                                                              denickeling (removal of nickel)                                               ratio               73%                                               ______________________________________                                    

EXAMPLES 19-21

On the same dried sepiolite as used in Examples 1-18 was sprayed a mixedsolution of a mixture of cobalt nitrate, nickel nitrate and ammoniumparamolybdate dissolved in an ammonia water to have the metals supportedthereon. The catalysts having different amounts of the metals supportedwere obtained by varying the concentration of the ammonium aqueousCo-Ni-Mo solution. After the catalysts thus obtained were calcined at500° C. for 2 hours, the activity of each catalyst was tested by usingthe same reaction apparatus and residual oil as employed in Examples1-18. Reaction was carried out under the reaction conditions of hydrogenpressure of 140 kg/cm², a reaction temperature of 400° C. and a liquidspace velocity of 2.0 Hr⁻¹ with upward flow.

The reaction activities of the catalysts 50, 500 and 1,000 hours afterstarting the reaction were determined by measuring devanadiuming ratio(DVR) and desulfurization ratio (DSR). The results are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Catalytic metal                                                                             Activity of catalyst                                            composition   after 50 hours                                                                       after 500 hours                                                                       after 1,000 hours                                Example                                                                            Co Ni Mo DVR DSR                                                                              DVR DSR DVR  DSR                                         Nos. (%)                                                                              (%)                                                                              (%)                                                                              (%) (%)                                                                              (%) (%) (%)  (%)                                         __________________________________________________________________________    19   1.6                                                                              0.5                                                                              4.0                                                                              64  24 61  21  52   20                                          20   3.5                                                                              1.1                                                                              7.2                                                                              73  32 70  29  62   22                                          21   4.3                                                                              1.6                                                                              11.3                                                                             78  39 72  31  63   20                                          __________________________________________________________________________

It is clear from the results shown in the table above thatdemetalization activity is enhanced as the amount of the metalssupported on the carrier increases.

REFERENCE EXAMPLES 1-4

These reference examples are intended to compare the catalytic activityof the present catalyst with those of the conventional desulfurizationcatalysts.

The same residual oil as used in Examples 19-21 was subjected tohydrotreating by using each of the conventional desulfurizationcatalysts for heavy oils, i.e. an activated bauxite catalyst and a redmud catalyst, under the same conditions as in Examples 19-21. Thedesulfurization catalysts for heavy oils employed herein comprised from3 to 3.5% of cobalt and 8 to 10% of molybdenum (these percentages arebased on the elemental metals) supported on alumina. The red mudcatalyst was a spheric catalyst 1.5 mm in diameter while the activatedbauxite catalyst had particle sizes of 6 to 20 mesh.

The catalytic activity of each catalyst is shown in Table 3. Also areshown in the table 3 the physical properties of each catalyst measuredaccording to mercury porosimeter method, said properties being relatedto the pores 78 A or more in diameter.

                                      TABLE 3                                     __________________________________________________________________________                  Catalytic activity   physical property                                        after  after  after  of catalyst                                              50 hours                                                                             100 hours                                                                            1,000 hours                                                                          pore                                                                              specific                               Reference                                                                            Catalyst                                                                             DVR DSR                                                                              DVR DSR                                                                              DVR DSR                                                                              volume                                                                            surface area                           Example Nos.                                                                         employed                                                                             (%) (%)                                                                              (%) (%)                                                                              (%) (%)                                                                              (cc/g)                                                                            (m.sup.2 /g)                           __________________________________________________________________________    1      desulfuriza-                                                                         64  75 40  46 13  22 0.40                                                                              168                                           tion catalyst                                                          2      desulfuriza-                                                                         69  73 58  55 29  35 0.66                                                                              160                                           tion catalyst                                                          3      red mud                                                                              24   5 22   6 19   4 0.18                                                                               9                                            catalyst*                                                              4      activated                                                                            41  12 34   8 28   7 0.25                                                                               32                                           bauxite                                                                __________________________________________________________________________     *When a red mud catalyst is employed, reaction must be generally carried      out at 420° C. or higher, the temperature being higher than the        case where a conventional desulfurization is employed. In order to compar     the catalyst with those of the present invention, however, the reaction       was carried out at 400° C.                                        

EXAMPLES 22-24

Each of 80:20, 50:50, and 20:80 mixtures of a sepiolite mineral ofSpanish product and a commercial available boehmite alumina was groundto particles 1 to 200μ in size, and admixed with 3% (as anhydride) of analuminium hydroxide sol. The water content of the resultant mixture wasadjusted, followed by molding into cylindrical pellets 0.8 to 1.0 mm indiameter by an extruder. Each of the pellets was air-dried, and thencalcined at 500° C. for 2 hours to obtain a catalyst carrier.

Catalysts were prepared by having copper, cobalt and molybdenumsupported on the carriers in the same way as in Examples 19-21, followedby calcining at 500° C. for 2 hours.

The catalytic activities of the catalysts thus prepared were testedunder the same conditions as in Examples 19-21, at a hydrogen pressureof 140 kg/cm², reaction temperature of 400° C., and liquid spacevelocity of 2.0 Hr⁻¹, in the same way as in Examples 19-21.

The results of the test 50 hours after starting the reaction are shownin Table 4. Also are shown in the table the pore volumes and thespecific surface areas of the pores 78 A or more in diameter containedin the catalysts which are measured according to mercury porosimetermethod.

                                      TABLE 4                                     __________________________________________________________________________                                      Physical property                                       Metals supported                                                                             Catalyst                                                                             of catalyst                                             (as metal)     activity                                                                             pore                                                                              specific                                Example                                                                            Sepiolite to                                                                         copper                                                                            cobalt                                                                            molybdenum                                                                           DVR DSR                                                                              volume                                                                            surface area                            Nos. alumina ratio                                                                        (%) (%) (%)    (%) (%)                                                                              (cc/g)                                                                            (m.sup.2 /g)                            __________________________________________________________________________    22   80:20  1.4 3.2 7.5    79  42 0.55                                                                              101                                     23   50:50  1.1 3.3 7.7    77  58 0.47                                                                              113                                     24   20:80  1.5 3.2 7.8    75  73 0.41                                                                              127                                     __________________________________________________________________________

It is apparent from the above results that the proportion ofdesulfurization ratio to demetallization ratio increased with thedecrease in the proportion of sepiolite to alumina.

EXAMPLES 25-27

Each of the metals listed in Table 5 was supported on a sepiolitecarrier in an amount of 1.0% (as metal). Namely, the carrier wassubjected to a conventional impregnating method using an aqueoussolution of the chloride or nitrate of each metal. Each of the metal onsepiolite-materials was calcined at 500° C. for 2 hours to obtain acatalyst. By using each of the catalysts thus obtained, topped resudialoil containing 150 ppm of vanadium and 2.87% of sulfur was subjected tohydrotreating at hydrogen pressure of 140 Kg/cm² and reactiontemperature of 400° C. The results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                        Catalyst                                                                      pore                 Catalytic activity                                            volume of           devanadiuming                                                                           desulfurization                            Ex.  carrier   metals    ratio     ratio                                      Nos. (cc/g)    supported (%)       (%)                                        ______________________________________                                        25   0.6       Cu + Zn   71         9                                         26   0.6       Ag        42        10                                         27   0.6       Sm        72        15                                         ______________________________________                                    

EXAMPLES 28-31

On each of the catalysts obtained in Examples 25, 26 and 27 wasadditionally supported Mo, Co or a mixture of Mo and Co in the amount(as metal) of 5%, 1.5% or 6.5% (Mo:5%+Co:1.5%) of the weight of theanhydrous carrier, respectively, by soaking each catalyst in an aqueoussolution of ammonium molybdate and/or cobalt nitrate in one stage,followed by calcining at 500° C. for 2 hours. By employing each of thecatalysts thus obtained, the same residual oil as used in Examples 25-27was subjected to hydrotreating under the same conditions as in theseexamples. The results are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Catalyst                                                                      supporting           Catalytic activity                                            catalyst            devanadiuming                                                                           desulfurization                            Ex.  (shown by metals    ratio     ratio                                      Nos. Ex. Nos.) supported (%)       (%)                                        ______________________________________                                        28   25        Mo + Co   88        59                                         29   25        Mo        86        35                                         30   26        Co        69        23                                         31   27        Mo + Co   84        58                                         ______________________________________                                    

EXAMPLE 32

As a sepiolite carrier, was employed a sepiolite mineral of Spanishproduct which had been regulated to have particle sizes within the rangeof 10 to 16 mesh. After drying at 200° C. for 2 hours, the sepiolite wassoaked in the aqueous solution of copper nitrate (pH 3.0) containing 0.5mol/l of Cu²⁺, held at 60° C. for 3 hours and then taken out from thesolution, and rinsed with warm water until no coloring due to thepresence of Cu²⁺ ions was observed in the rinsings. The analysis of theresultant copper on sepiolite-product, which had been dried at 200° C.,showed that it contained 1.7% of Cu (as metal).

The dried copper on sepiolite-product was then soaked in an aqueousammonium solution of ammonium paramolybdate and cobalt nitrate, followedby calcining at 500° C. for 2 hours. The analysis of the resultantCu-Co-Mo on sepiolite-catalyst showed that it contained 3.4% of cobaltand 7.9% of molybdenum (as metals).

By using the catalyst thus obtained, a topped residual oil containing2.62% of sulfur, 3,600 ppm of nitrogen, 3.2% of n-heptane-insolublematter was subjected to hydrotreating using a conventional high pressureflow-type reactor at hydrogen pressure of 140 kg/cm², reactiontemperature of 400° C., and liquid space velocity of 0.5 Hr⁻¹. Thetreated oil 100 hours after starting the reaction was analysed. Theresults are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Results analysed                                                              S %          N.sub.ppm                                                                            V.sub.ppm                                                                              Ni.sub.ppm                                                                          asphaltenes %                              ______________________________________                                        treated oil                                                                           0.8      2,600   6      1    0.5                                      residual oil                                                                          2.62     3,600  130    34    .[.--.]..Iadd.3.2.Iaddend.               ______________________________________                                    

REFERENCE EXAMPLE 5

A Cu, Co and Mo on sepiolite-catalyst was prepared by impregnating thesame sepiolite as used in Example 32 in an aqueous ammonium solutioncontaining ammonium paramolybdate, cobalt nitrate and copper nitrateaccording to a conventional impregnating method. The analysis of thecatalyst after sintering showed that 2.0% of copper, 3.3% of cobalt and8.2% of molybdenum were supported thereon.

By using the catalyst thus obtained, hydrotreating was carried out byemploying the same starting material, apparatus and reaction conditionsas employed in Example 32. In Table 8 are shown the results of theanalysis of the treated oil together with those of Example 32 forcomparison.

                  TABLE 8                                                         ______________________________________                                                   Results analysed                                                             S       N      V      Ni  Asphaltene                                Catalyst  %       ppm    ppm    %   %                                         ______________________________________                                        Reference 1.2     3,100  15     12  0.7                                       Example 5                                                                     Example 32                                                                              0.8     2,600   6      1  0.5                                       ______________________________________                                    

EXAMPLES 33-39

A metals on sepiolite-catalyst was prepared by repeating the procedureof Example 32 except changing the treating solutions of the metalcompounds to be used in the first step and the second step. In the firststep, the dried sepiolite was treated to have 1 to 3% of Fe, Ni, Zn, Smor La supported thereon by using a corresponding aqueous solution offerric sulfate, nickel nitrate, zinc chloride, samarium, chloride, orlanthanum chloride. Then, in the second step, each of the resultantmetal on sepiolite-base catalyst was further treated to have two orthree of Mo, W, V, Co, Ni, and Cu supported thereon by using an aqueoussolution of the corresponding two or three compounds selected fromammonium paramolybdenum, ammonium, paratungstate, ammonium vanadate,cobalt nitrate, nickel nitrate and copper nitrate.

By using each of the catalysts thus obtained, hydrotreating was carriedout by employing the same residual oil and the same reaction conditionsas in Example 32. The results of the analysis of produced oil 100 hoursafter starting the reaction are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                        Catalyst metal                                                                first step      second step                                                             amount         amount  Result analysis                                        of             of      of treated oil                               Example                                                                              catalytic                                                                              metal   catalytic                                                                            metal S     V                                  Nos.   metal    (%)     metal  (%)   (%)   (ppm)                              ______________________________________                                        33     Fe       2.3     Co     1.2   1.6   13                                                         Mo     2.7                                                                    Co     1.5                                            34     Ni       1.9     Mo     2.6   1.2   11                                                         Cu     1.0                                            35     Ni       1.9     Co     0.7   1.7   3                                                          Mo     11.7                                           36     Za       1.1     Co     1.2   1.5   2.4                                                        V      7.2                                            37              0.7     Co     2.3   1.4   21                                                         Mo     4.1                                            38     La       1.2     Co     1.5   0.8   4                                                          W      10.9                                           39     La       1.2     Ni     3.4   0.5   1                                                          Co     1.8                                                                    Mo     14.9                                           residual                              2.62 130                                oil                                                                           ______________________________________                                    

EXAMPLE 40

A sepiolite of Spanish product was employed as the starting materialafter regulating the particle sizes thereof within the range of 10 to 16mesh. The sepiolite was dried at 120° C. for 2 hours, impregnated in theaqueous solution containing 0.01 mol/l of ammonium nitrate, and thenallowed to stand at room temperature for a whole day and night. Afterthe sepiolite treated with ammonium nitrate was thoroughly washed withwater, the moist sepiolite was soaked in the aqueous solution containing0.01 mol/l of copper nitrate, and then allowed to stand at roomtemperature to have copper supported thereon. The resultant copper onsepiolite-material was washed with warm water and then with 10% ammoniawater to remove unexchanged copper ions and magnesium ions. The analysisof the resultant sepiolite material, which had been dried at 200° C. for2 hours, showed that 2.1% of copper (as the oxide) was containedtherein.

The copper on sepiolite-material was then impregnated in the aqueoussolution containing 16% of ammonium paramolybdenum and 10% of ammonia tohave molybdenum supported thereon. The sepiolite material thus treatedwas dried at 120° C. for 2 hours, and calcined at 500° C. for 1 hour.The analysis of the resultant catalyst showed that 2.2% of CuO and 8.6%of MoO₃ were contained therein.

By using the catalyst thus obtained, a topped residual oil containing2.62% of sulfur, 3,600 ppm of nitrogen, 3.2% of n-heptane-insolublematter, 130 ppm of vanadium and 34 ppm of nickel was subjected tohydrotreating at hydrogen pressure of 140 kg/cm², reaction temperatureof 400° C., and liquid space velocity of 0.5 Hr⁻¹. The analysis of thetreated oil 100 hours after starting the reaction showed that theamounts of the impurities in the residual oil were decreased to 0.70% ofsulfur, 2,400 ppm of nitrogen, 6 ppm of vanadium, 5 ppm of nickel and0.5% of n-heptane-insoluble matter.

EXAMPLE 41

The same sepiolite as used in Example 40 was dried at 120° C. for 2hours, then impregnated in the aqueous solution containing 0.1 mol/l ofammonium chloride and 0.1 mol/l of cobalt nitrate, and allowed to standat room temperature for 5 hours to have cobalt supported thereon.

The resultant cobalt on sepiolite-material was washed thoroughly withwarm water to remove unexchanged cobalt ions and magnesium ionstherefrom, followed by drying at 200° C. for 2 hours. The dried materialwas impregnated with the aqueous solution containing 10% of ammoniumparamolybdate and 10% of ammonia, and then dried at 120° C. for 2 hours.The analysis of the catalyst thus obtained showed that 1.3% of CoO and6.5% of MoO₃ were contained therein.

By employing the catalyst, the same residual oil as used in Example 40was subjected to hydrotreating using the same apparatus as in Example40. Reaction conditions were identical with those of Example 40 exceptthat the liquid space velocity was changed to 1.0 Hr⁻¹. The analysis ofthe treated oil 100 hours after starting the reaction showed that theamounts of sulfur and vanadium were decreased to 1.57% and 36 ppm,respectively.

EXAMPLE 42

The same sepiolite as used in Example 40 was dried at 120° C. for 2hours and then incorporated with the aqueous solution containing 0.1mol/l of acetic acid, followed by thoroughly stirring the mixture forabout 2 hours. To the sepiolite thus treated with acetic acid was addedthe aqueous solution containing 0.1 mol/l of lanthanum nitrate and 0.02mol/l of nickel nitrate. The resultant mixture was allowed to stand forabout 3 hours to obtain lanthanum and nickel on sepiolite material,which was sufficiently rinsed with warm water and then dried at 200° C.for 1 hour. The analysis of the resultant dried material showed that1.2% of La₂ O₃ and 1.4% of NiO were contained therein.

The dried lanthanum and nickel on sepiolite material was impregnatedwith the aqueous solution containing 3.0% of ammonium paratungstate and5% of ammonia and then dried at 200° C., followed by repeating theimpregnating and drying, to have tungsten supported on the sepiolitematerial. The resultant lanthanum, nickel and tungsten on sepiolitematerial was calcined at 500° C. for 1 hour to obtain a catalyst forhydrotreating. The analysis of the catalyst showed that 1.1% of La₂ O₃,1.3% of NiO and 9.8% of WO₃ were contained therein.

By employing this catalyst, the same residual oil as used in Example 40was subjected to hydrotreating by the same reaction apparatus as used inExample 40. Reaction was carried out at hydrogen pressure of 160 kg/cm²,a reaction temperature of 430° C. and a liquid space velocity of 2.0Hr⁻¹. The analysis of the treated oil 100 hours after starting thereaction showed that the amounts of vanadium, sulfur and nitrogen weredecreased to 19 ppm, 1.20% and 2,800 ppm, respectively. By a reducedpressure distillation of the treated oil, the fraction distillated atlower than 550° C. was obtained in the yield of 81% by volume (whereas,the same fraction yield of the feeded residual oil was 63% by volume).Thus, it is recognized that the catalyst according to the presentinvention has a very high activity in not only desulfurization,denitrification and demetallization but also hydrocracking of heavyoils.

EXAMPLES 43 and 44

By employing the Co and Mo on sepiolite-catalyst, a vacuum oilcontaining 2.0% of sulfur and a cracked gas oil having a bromine numberof 26 and 2.6% sulfur (distillated at 200°-500° C.) was subjected tohydrotreating. The reaction was carried out under hydrogen pressure of30 kg/cm², at a temperature of 380° C. and a liquid space velocity of1.0 Hr⁻¹ by the same reaction apparatus as used in Example 40. Theanalysis of the treated oils 50 hours after starting the reactionsprovided the following results as shown in Table 10.

                  TABLE 10                                                        ______________________________________                                                            Results 50 hrs. after starting                            Example Starting    reactions                                                 Nos.    Material oils                                                                             sulfur content                                                                            bromine number                                ______________________________________                                        43      vacuum gas oil                                                                            0.50%       --                                            44      cracked gas oil                                                                           1.42%       12                                            ______________________________________                                    

From these results, it is shown that the catalyst obtained according tothe present invention is effective for the desulfurization byhydrogenation of light oils as well as heavy oils and for decrease inbromine number of cracked oils by hydrogenation thereof.

EXAMPLE 45

The same sepiolite as used in Example 40 was employed as the startingmaterial. The sepiolite was soaked in the aqueous solution containing0.1 mol/l of magnesium nitrate and allowed to stand at room temperaturefor 5 hours, followed by a sufficient rinse with warm water. The rinsedsepiolite was impregnated in the aqueous solution containing 0.01 mol/lof nickel nitrate for 2 hours to have nickel supported thereon. Theresultant nickel on sepiolite material was sufficiently rinsed with warmwater and then with 10% ammonia water, followed by drying at 200° C. for2 hours. The dried material was impregnated in the aqueous solutioncontaining 4% of ammonium vanadate and 4% of ammonia and dried at 120°C. for 1 hour followed by sintering at 500° C. for 1 hour. The analysisof the resultant catalyst showed that 0.8% of NiO and 6.1% of V₂ O₅ werecontained therein.

By employing this catalyst, the same residual oil as used in Example 40was subjected to hydrotreating using the same apparatus as in Example40, under the same reaction conditions as employed in Example 41. Theanalysis of the treated oil 100 hours after starting the reaction showedthat the sulfur and the vanadium contents were decreased to 1.64% and 34ppm, respectively.

REFERENCE EXAMPLE 6

A Co and Mo on sepiolite-catalyst was prepared by employing as thestarting material the same sepiolite as used in Example 40, by changingthe process for preparation. The starting material sepiolite wasimpregnated in a mixed aqueous ammonium solution of cobalt nitrate andammonium paramolybdate which had been adjusted to a predeterminedconcentration, followed by baking at 500° C. for 1 hour. The analysis ofthe resultant catalyst showed that 1.7% of CoO and 5.9% of MoO₃ werecontained therein.

By employing this catalyst, Example 43 was repeated to subject the samevacuum distillation light oil to desulfurization. The analysis of thetreated oil 50 hours after starting reaction showed that 0.97% of sulfurwas contained therein.

REFERENCE EXAMPLE 7

A Co and Mo on sepiolite-catalyst was prepared in the same way as inReference Example 6. The starting material sepiolite was dried at 120°C. for 2 hours, impregnated in the aqueous solution containing 0.1 mol/lof ammonium nitrate and 0.1 mol/l of cobalt nitrate and allowed to standat room temperature for 5 hours. The Co on sepiolite-material as takenout without a further rinse was dried at 200° C. for 2 hours and thentreated substantially in the same way as in Example 41 to havemolybdenum supported thereon. The analysis of the resultant catalystshowed that 1.4% of CoO and 6.3% of MoO₃ were contained therein.

By employing this catalyst, Example 43 was repeated to subject thevacuum gas oil to desulfurization. The analysis of the treated oil 50hours after starting reaction showed that 0.68% of sulfur was containedtherein. From the result, it is understood that the residues of theunexchanged cobalt and water-soluble magnesium salt or the sepiolitematerial, which were caused by avoiding the rinsing treatment, gave anadverse effect on the activity in hydrotreating to the resultantcatalyst.

REFERENCE EXAMPLE 8

A copper and Mo on sepiolite catalyst was prepared substantially in thesame way as in Example 40 using the same sepiolite as the startingmaterial. In Example 40, the sepiolite was treated with the aqueoussolution containing 0.01 mol/l of ammonium nitrate before the step ofhaving each metal supported thereon; however, in this Example, thetreatment with the ammonium nitrate solution was avoided. The analysisof the resultant catalyst showed that 2.0% of CuO and 9.1% of MoO₃ werecontained therein.

By employing this catalyst, Example 40 was repeated to subject the sameresidual oil to hydrotreating. The analysis of the treated oil 100 hoursafter starting reaction showed that 0.92% of sulfur content, and 9 ppmof vanadium were contained therein. By comparing this result with thatobtained in Example 40, it is understood that the demetallizationactivity of the resultant catalyst was enhanced by treating thesepiolite with an ammonium nitrate solution in the course of preparationof the catalyst.

EXAMPLES 46-52

As the starting material was employed the sepiolite mineral of Spanishproduct having a specific surface area of 170 m² /g, a pore volume of0.59 cc/g, and a pore ratio of 25% in the range of 200 to 400 A in porediameter (that is, the pores in the sepiolite, 200 to 400 A in porediameter, accounting for 25% of the pore volume). The sepiolite wasdried at 200° C. for 3 hours, and ground in a ball mill until all of itattained fineness of 50 mesh or more, more than about 70% of it havingfineness of more than 100 mesh. The dried sepiolite powder wasincorporated with an aluminium hydroxide sol containing 17% of anhydrousalumina in such an amount as to make the ratio of anhydrous alumina todry sepiolite 5%, and the water content of the mixture was adjusted to150% by adding water thereto. The resulting moist mixture was wellkneaded by an extruder. The number of passes through the extruder forkneading was determined in such a way that the products as extruded,each of which was passed through the extruder a different number oftimes, was calcined at 500° C., respectively, and after their porevolumes had beforehand been measured, the number of passes which gavethe maximum pore volume was taken as the goal.

According to observation on photomicrographs (magnification×10,000) byelectron microscope of the kneaded mixture, it was confirmed that thefascicles of sepiolite fibers were got untied to separate fibers in thecase where the kneaded mixture had the maximum pore volume.

The kneaded mixture was molded into cylindrical pellets about 1.0 mm indiameter by a conventional extruder, which were sufficiently air-driedand then calcined at 500° C. for 3 hours to obtain porous sepiolitecarriers.

The carriers were subjected to a conventional one-liquid or two-liquidtreatment to have Cu, Zn, Ce, V, Mo, Ni and/or Co components supportedon the carriers by utilizing ammonium metavanadate for V, ammoniumparamolybdate for Mo and the corresponding nitrates for the othermetals. The carriers thus treated were calcined at 500° C. for 1 hour toobtain the catalysts shown in Table 11. Each of these catalysts had aspecific surface area (BET method) of 180 to 210 m² /g, pore volume of0.75 to 0.8 cc/g, and pore volume ratio of 40 to 55% in the range of 200to 400 A in pore diameter.

Each of these catalysts was packed in a high pressure flow-type reactor.A topped residual oil containing 2.87% of sulfur content, 3,600 ppm ofnitrogen content, 3.0% of n-heptane-insoluble matter, 150 ppm ofvanadium, 41 ppm of nickel, and 3 ppm of iron, was subjected tohydrotreating using the reactor at hydrogen pressure of 140 kg/cm², areaction temperature of 400° C. and a liquid space velocity of 2.0 Hr⁻¹,with upward flow. The results are shown in Table 11.

From these results, it is clearly shown that the catalyst of the presentinvention has a very high activity and that the residual oil containinga large amount of metals can be treated over a long period of timeaccording to the method of the present invention.

                                      TABLE 11                                    __________________________________________________________________________    Catalytic metal   Activity of catalyst                                        Example                                                                            composition  after 50 hours  after 500 hours                             Nos. component                                                                           % (as metal)                                                                         DSR.sup.(1)                                                                       DVR.sup.(2)                                                                       DNR.sup.(3)                                                                       DAR.sup.(4)                                                                       DSR.sup.(1)                                                                       DVR.sup.(2)                             __________________________________________________________________________    46         2      13  42  <10 21   9  35                                                 6                                                                  47   Cu    12     11  32  10  24  10  29                                           Sn    12                                                                      Ce    2                                                                  48   Mo    6      17  51  12  27  15  40                                           Ni    2                                                                  49   V     6      14  47  14  27  12  36                                           Co    3.5                                                                50   Ni    1.0    29  65  19  35  21  58                                           Mo    7.5                                                                     Ni    2.4                                                                51   Co    1.4    31  65  17  31  26  59                                           Mo    15.0                                                                    Co    1.5                                                                52   Mo    4.8    37  70  19  42  24  62                                      __________________________________________________________________________     Note:                                                                         .sup.(1) DDR: desulfurization ratio %                                         .sup.(2) DVR: devanadiuming (removal of vanadium) ratio %                     .sup.(3) DNR: denitrification ratio %                                         .sup.(4) DAR: deasphaltening (removal of asphaltene) ratio %             

EXAMPLE 53

A porous magnesium-silica carrier was prepared in the same way as inExamples 46-52 except that aluminium sulfate instead of aluminiumhydroxide sol was added to dry sepiolite in such an amount as to makethe ratio of anhydrous alumina to the sepiolite 2.0%, water was added tothe mixture to adjust the water content thereof to 135%, and the moldedpellets were calcined at 800° C. for 3 hours.

The catalyst of the present invention was obtained by treating theresultant carrier with cobalt nitrate and paramolybdic acid according toa conventional method, to have 2% of cobalt and 6% of molybdenumsupported on the carrier.

By employing the resultant catalyst, the same residual oil as used inExamples 46-52 was subjected to hydrotreating, at hydrogen pressure of110 kg/cm², reaction temperature of 370° C., and liquid space velocityof 0.8 Hr⁻¹. Activity of the catalyst 50 hours after starting thereaction was measured, which is shown in the following:

devanadiuming ratio: 61%

denickling (removal of nickel) ratio: 48%

deironing (removal of iron) ratio: 64%

desulfurization ratio: 24%

EXAMPLE 54

A porous magnesia-silica carrier was obtained in the same way as inExamples 46-52 except that aluminium hydroxide sol was added to drysepiolite in such an amount as to make the ratio of anhydrous alumina todry sepiolite 3.0%, copper nitrate was further added thereto in such anamount as to make the ratio of copper to sepiolite 4%, water was addedto the mixture to adjust the water content thereof to 145%, the kneadedmixture was molded into cylindrical pellets of 1.5 mm in diameter, andcalcining was carried out at 400° C. for 3 hours.

The resultant carrier was treated with an aqueous solution of ammoniumparamolybdate according to a conventional method to have 6% ofmolybdenum supported on the carrier. The carrier thus treated was thencalcined at 600° C. for 1 hour to obtain a catalyst of the presentinvention.

By employing the resultant catalyst, the same residual oil as used inExamples 46-52 was subjected to hydrotreating, at hydrogen pressure of140 kg/cm², reaction temperature of 400° C., and liquid space velocityof 0.5 Hr⁻¹. Activities of the catalyst 50 hours and 1,000 hours afterstarting the reaction are shown in the following.

    ______________________________________                                                       after 50 hours                                                                         after 1,000 hours                                     ______________________________________                                        devanadiuming ratio (%)                                                                        97         83                                                denickeling ratio (%)                                                                          88         75                                                deironing ratio (%)                                                                            58 or more 91                                                desulfurization ratio (%)                                                                      74         57                                                denitrification ratio (%)                                                                      57         32                                                ______________________________________                                    

EXAMPLE 55

The catalyst of the present invention was prepared in the same way as inExamples 46-52 except that cobalt nitrate instead of the aluminiumhydroxide sol was added to dry sepiolite in such an amount as to makethe ratio of cobalt to sepiolite 3.0% followed by addition of water toadjust the water content thereof to 120%, ammonium paramolybdate wasadded to the moist mixture in such an amount as to make the ratio ofmolybdenum to sepiolite 9% followed by kneading and molding the mixtureinto pellets (instead of adding the catalytic metals to the moldedcarrier), and calcining was carried out at 500° C. for 3 hours. Theresultant porous magnesia-silica catalyst containing cobalt andmolybdenum had the following physical properties:

specific surface area (BET method): 216 mg² g

pore volume (>74 A): 0.522 cc/g

pore ratio (200 A-400 A in diameter): 76%

By employing this catalyst, the same residual oil as used in Examples46-52 was subjected to hydrogenation treatment, at hydrogen pressure of140 kg/m², a reaction temperature of 370° C. and a liquid space velocityof 0.8 Hr⁻¹. Activity of the catalyst 50 hours after starting thereaction is shown in the following.

devanadiuming ratio: 53%

denickling ratio: 40%

desulfurization ratio: 19%

EXAMPLE 56

A porous magnesia-silica carrier was obtained in the same way as inExamples 46-52 except that, in the course of the moistening step, aceticacid was added together with aluminium hydroxide sol and water to drysepiolite to adjust the pH of the mixture to 4.0.

The resultant carrier was treated with aqueous solutions of nickelnitrate, cobalt nitrate and ammonium paramolybdate according to aconventional impregnating process, to have cobalt, nickel and molybdenumsupported on the carrier. The treated carrier was sintered at 600° C.for 1 hour to obtain a catalyst of the present invention. The propertiesof the catalyst are shown in the following.

    ______________________________________                                        amounts of metals supported (as metal)                                                                Ni      2.4%                                                                  Co      1.5%                                                                  Mo      14.5%                                         specific surface area (BHT method)                                                                            226 m.sup.2 /g                                pore volume (>74 A)             0.62 cc/g                                     pore ratio (200A-400A in diameter)                                                                            66%                                           ______________________________________                                    

By employing this catalyst, the same residual oil as used in Examples46-52 was subjected to hydrotreating, at hydrogen pressure of 140kg/cm², reaction temperature of 400° C., and liquid space velocity of2.0 Hr⁻¹. The results are shown in the followings:

    ______________________________________                                                         after starting the reaction                                                   50 hours                                                                             500 hours                                             ______________________________________                                        devanadiuming ratio %                                                                            75       63                                                denickeling ratio %                                                                              61       43                                                desulfurization ratio %                                                                          33       21                                                denitrification ratio %                                                                          16       12                                                ______________________________________                                    

EXAMPLE 57

A porous magnesia-silicate carrier was obtained in the same way as inExamples 46-52 except that, in the course of the moistening step, acidclay containing 60% of SiO₂ and 15% of Al₂ O₃ was added to the drysepiolite in place of aluminum hydroxide sol in such an amount as tomake the ratio of acid clay to sepiolite 5%, water was added thereto toadjust the water content to 160%, and the moist mixture was molded intocylindrical pellets 1.5 mm in diameter followed by calcining at 400° C.for 3 hours.

The resultant carrier was treated with aqueous solutions of nickelnitrate and ammonium paratungstate according to a conventionalimpregnating process, to have the nickel and tungsten compoundssupported on the carrier in the amounts of 5.1% and 12.7% as metals,respectively. The treated carrier was calcined at 600° C. for 1 hour.The main properties of the resultant catalyst are shown in the following

specific surface area (BET method): 175 m² /g

pore volume (>74 A): 0.76 cc/g

pore ratio (200 to 400 A in diameter): 51%

By employing this catalyst, the same residual oil as used in Examples46-52 was subjected to hydrotreating, at a hydrogen pressure of 160kg/cm², a reaction temperature of 400° C. and liquid space velocity of0.8 Hr⁻¹, to obtain the following results.

    ______________________________________                                                       after starting the reaction                                                   50 hours                                                                             1,000 hours                                             ______________________________________                                        devanadiuming ratio                                                                            98       78                                                  denickeling ratio                                                                              79       56                                                  desulfurization ratio                                                                          67       43                                                  ______________________________________                                    

As the comparative or reference examples, are shown in the following theresults obtained by carrying out the reactions under the sameconditions, by employing the catalyst of cobalt and molybdenum supportedon a conventional alumina carrier or the catalyst which was prepared byhaving cobalt, nickel and molybdenum supported on untreated sepiolitemineral of 6 to 20 mesh in fineness.

REFERENCE EXAMPLES 9-11

The conventional desulfurization catalysts (I) and (II) were prepared byhaving 3 or 3.5% (hereinafter as metal) of cobalt and 8 or 10% ofmolybdenum supported on alumina carrier. The other catalyst was preparedby having 3.5% of cobalt, 1.1% of nickel and 7.2% of molybdenumsupported on the untreated sepiolite having a specific surface area (BETmethod) of 154 m² /g and pore volume (>74 A) of 0.52 cc/g.

By employing these catalysts, the same residual oil as used in Examples46-52 was subjected to hydrotreating, at hydrogen pressure of 140kg/cm², reaction temperature of 400° C. and liquid space velocity of 2.0Hr⁻¹, with upward flow. The results are shown in Table 12.

From these results, it is clearly shown that the catalysts according tothe present invention have a markedly large demetallization (removal ofmetals) activity and a longer life of catalytic activity.

When compared with the untreated sepiolite carrier, the catalyst of thepresent invention has a larger demetallization activity even when theamounts and kinds of the catalytic metals are identical. Also incomparison with the physical properties of these catalysts, the presentcatalysts have a markedly larger specific surface area and pore volume.

                                      TABLE 12                                    __________________________________________________________________________                   After starting the treatment                                   Reference                                                                            Catalyst                                                                              50 hours                                                                              500 hour                                                                              1,000 hours                                    Example Nos.                                                                         employed                                                                              DVR*                                                                              DSR**                                                                             DVR*                                                                              DSR**                                                                             DVR*                                                                              DSR**                                      __________________________________________________________________________     9     desulfurization                                                                       64  75  40  46  13  22                                                catalyst (I)                                                           10     desulfurization                                                                       69  73  58  55  29  35                                                catalyst (II)                                                          11     catalyst with                                                                         73  32  70  29  62  22                                                sepiolite                                                              __________________________________________________________________________     *DVR: devanadiuming ratio %                                                   **DSR: desulfurization ratio %                                           

EXAMPLE 58

A crushed sepiolite of Spanish product 1 to 2 mm in diameter wasemployed as the starting material. The sepiolite was dried at 200° C.for 3 hours and then subjected to dry milling in a ball mill to such anextent that finely divided powder of 100 mesh or more was obtained in anamount of about 70% of the whole powder, the coarse powder of largerthan 50 mesh being sieved off.

Aluminium hydroxide sol containing 17% of alumina was added to thesepiolite powder in such an amount as to make the ratio of aluminacontent to dry sepiolite 5% and then water was added thereto to adjustthe water content thereof to about 150%, to obtain rather hard paste.The paste was fully kneaded by passing it through an extruder threetimes, followed by molding it into cylindrical pellets 1.0 mm indiameter by the extruder. The pellets were air-dried and then calcinedat 500° C. for 3 hours to obtain molded product. The properties of theresultant product are shown in Table 13 in comparison with those of thestarting material sepiolite (dried at 200° C.).

                  TABLE 13                                                        ______________________________________                                                           molded starting                                                               sepiolite                                                                            material                                            ______________________________________                                        (1)   specific surface area                                                                            216      170                                               (BET method, m.sup.2 /g)*                                                     specific surface area >74 A                                                                      113      71                                                (m.sup.2 /g)                                                                  distribution thereof                                                           74-200 A          33       29                                                200-600 A          73       31                                                >600 A             7        11                                          (2)   pore volume >74 A (cc/g)                                                                         0.83     0.59                                              distribution thereof                                                           74-200 A          0.13     0.11                                              200-600 A          0.62     0.27                                              >600 A             0.08     0.21                                        (3)   crushing strength (kg)                                                                           1.2-1.8  --                                          (4)   soaking in a aqueous                                                                             homo-    unhomo-                                           solution of cobalt geneous  geneous                                           nitrate            coloring coloring                                    ______________________________________                                         *calcined at 500° C. for the purpose of the comparison with the        molded sepiolite.                                                        

Incidentally, the difference in coloring after impregnating in anaqueous solution of cobalt nitrate (4) in Table 13 is due to thedifference in homogenuity of the cobalt-supporting on the sepiolite,which indicates that cobalt was homogeneously supported on the moldedsepiolite.

EXAMPLE 59

A molded sepiolite was obtained in the same way as in Example 58 exceptthat, in the course of moistening step, the aluminium hydroxide sol wasadded to the sepiolite powder in such an amount as to make the ratio ofanhydrous alumina to dry sepiolite 1.5% and an aqueous nitric acidsolution containing 0.1 mol/l of nitric acid was added thereto insteadof pure water to adjust the water content thereof to 120%. The calcinedproduct had the following properties.

(1) specific surface area (BET method): 250 m² /g

(2) pore volume >74 A:0.58 cc/g

As to the distribution of pore, most of large pores 600 A or more indiameter were disappeared, and the pores 200 to 400 A in diameteraccounted for about 70% of the whole pure volume.

(3) crushing strength: 4.6-6.0 kg

The molded product obtained in this Example was subjected to X-raydiffraction analysis, the pattern of which clearly showed a peak in theneighborhood of 2θ=7°, and it was assured that the molded product ofthis invention was converted to thermaly stable forms.

EXAMPLE 60

A molded product was prepared in the same way as in Example 58 exceptthat aluminium nitrate instead of the aluminium hydroxide sol was addedto the sepiolite powder in such an amount as to make the ratio ofaluminium metal to dry sepiolite 3.0%, water content was adjusted to130%, and sintering was carried out at 800° C. The sintered product hadthe following properties.

(1) specific surface area (BET method): 237 m² /g

(2) pore volume >74 A: 0.49 cc/g

(3) crushing strength: 4.7-7.5 kg

From these results, it is evident that the molded product has a rathersmaller pore volume, but has a larger specific surface area and markedlylarger crushing strength.

EXAMPLES 61-63

Molded products were obtained in the same way as in Example 58 exceptthat, in the course of moistening step, the aluminium hydroxide sol wasadded to the sepiolite powder in such an amount as to make the ratio ofanhydrous alumina to dry sepiolite 1.5%, an aqueous solution of coppernitrate, cerium chloride or nickel sulfate was added thereto instead ofpure water in an amount of 2% as Cu, Ce or Ni on the basis of drysepiolite, respectively, and the water content thereof was adjusted to130%. The sintered products had the following properties as shown inTable 14.

                  TABLE 14                                                        ______________________________________                                                         Example Nos.                                                                  61      62      63                                           ______________________________________                                        (1) additives (metal salts)                                                                          Cu(NO.sub.3).sub.2                                                                      CeCl.sub.3                                                                          NiSO.sub.4                             (2) specific surface area                                                                            241       249   232                                        (BET method, m.sup.2 /g)                                                  (3) pore volume (>74 A, cc/g)                                                                        0.55      0.57  0.58                                   (4) crushing strength (kg)                                                                           5.0-6.5   4.7-6.0                                                                             3-5.0                                  ______________________________________                                    

Measurements of the pore distribution clearly showed that most of thelarge pores of more than 600 A in diameter disappeared in these moldedproducts and the pores in the range of 200 to 400 A in diameteraccounted for 70 to 80% of the whole pore volume and has a very sharpdistribution curve. The X-ray diffraction patterns showed that theproducts were thermally stable since the peaks in the neighborhood of2θ=7° were scarcely lowered.

EXAMPLE 64

A molded product was obtained in the same way as in Example 58 exceptthat cobalt nitrate was added to the sepiolite powder in such an amountas to make the ratio of cobalt metal to dry sepiolite 3.0%, pure waterwas added thereto to adjust the water content thereof to 120%, and thenammonium molybdate was further added thereto in such an amount as tomake the ratio of molybdenum metal to dry sepiolite about 9%. Thecalcined product had the following properties.

(1) specific surface area (BET method): 216 m² /g

(2) pore volume (>74 A): 0.52 cc/g

(3) pore distribution (ratio in the range of 200 to 400 A): 76%

(4) crushing strength: 3.0-4.5 kg

EXAMPLE 65

Sepiolite of Korean product was crushed to the fineness 4 to 5 mm indiameter to be employed as the starting material. The crushed sepiolitewas impregnated for two days and nights in the aqueous solutioncontaining 0.1 mol/l of nickel nitrate and then sufficiently washed withwarm water maintained at 50° C. Incidentally, the resultant nickel onsepiolite was calcined at 500° C. for 2 hours and the analysis thereofshowed that 2.1% of nickel oxide was contained therein. According to theanalysis of the aqueous nickel nitrate solution in which sepiolite wassoaked, magnesium was dissolved therein in an amount about 2.6 times(atomic ratio) as much as that of nickel supported on sepiolite.

Then, about 3 parts of water was added to one part of the nickel onsepiolite-material, and the resultant mixture was well kneaded bykneader. Through this kneading step, the crushed sepiolite was ground topowder. After the mixture was kneaded enough to provide it with moldingproperty, the kneaded mixture was dried at 60° C. for a short time,followed by addition of water to adjust the water content thereof toabout 130%. The moist mixture was kneaded again for such a short timethat the water content did not change, and then molded into cylindricalpellets 1.7 mm in diameter. The molded pellets were air-dried for about5 days in the air and then calcined at 500° C. for 1 hour to obtain anickel on sepiolite-catalyst. The physical properties of the resultantcatalyst as well as those of the starting sepiolite which was calcinedat 500° C. for 1 hour are shown in Table 15.

                  TABLE 15                                                        ______________________________________                                                                   starting                                                            nickel on repio-                                                                        material                                                            lite-catalyst                                                                           sepiolite                                                           (calcined at                                                                            (calcined at                                                        500° C.)                                                                         500° C.)                                    ______________________________________                                        specific surface area                                                         (BHT method)       232 m.sup.2 /g                                                                            153                                            specific surface are                                                          (mercury peromimeter                                                          method >30 A)      133 m.sup.2 /g                                                                            65                                             pore volume (mercuryporo-                                                     simeter method >30 A)                                                                            0.68 cc/g   0.52                                           pore distribution (mercury)                                                   poresimeter method (>30 A)                                                     30-200 A          0.19 cc/g   0.12                                           200-600 A          0.44 cc/g   0.20                                           600 A              0.05 cc/g   0.18                                           crushing strength  3.5                                                        (radical direction)                                                                              5.0 kg      --                                             ______________________________________                                    

From Table 15, it will be understood that the nickel on sepiolite moldedcatalyst obtained according to the present invention has the physicalproperties significantly different from those of the starting materialsepiolite. That is, the molded product of the invention has (1) a largerspecific surface area, (2) a larger pore volume, and (3) a sharperdistribution curve, in comparison with the starting material sepiolite.The nickel on sepiolite molded product is clearly different in propertyfrom the product obtained by merely having nickel supported on thestarting material sepiolite. Thus, it would be understood that thetreatment procedure for sepiolite according to the present invention isquite different from a mere molding procedure (conventional carriers).

A cracked petroleum oil (boiling point: 200°-500° C.) containing 2.4% ofsulfur and 14 ppm of vanadium and having bromine number 26 was subjectedto hydrotreating by employing this catalyst. Reaction was carried out byusing a conventional flow-type high pressure reactor at a reactiontemperature of 360° C., hydrogen partial pressure of 50 kg/cm² andliquid space velocity of 1.0 Hr⁻¹. The analysis of the treated oil 50hours after starting the reaction showed the decreases in sulfur to2.1%, vanadium to 5 ppm and bromine number to 16.

EXAMPLE 66

The nickel on sepiolite molded catalyst which had been obtained inExample 65 was air-dried and then baked at 200° C. for 1 hour. The bakedproduct was impregnated in an aqueous ammonium solution of ammoniumparamolybdate and then calcined at 500° C. for 1 hour, to obtain anickel and molybdenum on sepiolite-catalyst. The analysis of the resultcatalyst showed that 2.0% of NiO and 5% of MoO₃ were contained therein.The physical properties of the catalyst measured in the same way as inExample 65 were similar to those of the catalyst obtained in Example 65,except that the specific surface area (BET method) and pore volume wereslightly decreased to 226 m² /g and 0.66 cc/g, respectively.

The same cracked petroleum oil as used in Example 65 was subjected tohydrotreating using the same apparatus under the same conditions as inExample 65, by employing the resultant catalyst. (That is, Example 65was repeated by employing this catalyst.) The analysis of the treatedoil showed the decreases in sulfur to 0.89%, vanadium to 3 ppm andbromine number to 14.

EXAMPLE 67

In the kneading step of the unformed (not molded) nickel onsepiolite-material in Example 65, a predetermined amount of ammoniumparatungstate was added thereto, to prepare a nickel and tungsten onsepiolite-catalyst. The kneading, moistening, molding and calciningsteps were carried out in the way and under the condition similar tothose of Example 65. The analysis of the resultant catalyst showed that2.0% of NiO and 7.8% of WO₃ were contained therein. The physicalproperties of the catalyst were similar to those of the catalystobtained in Example 65, as in the case of Example 64.

By employing this catalyst, a topped residual oil containing 2.62% ofsulfur, 3,600 ppm of nitrogen, 3.2% of n-heptane-insoluble matter, 130ppm of vanadium, and 41 ppm of nickel was subjected to hydrotreatingusing the same reaction apparatus as in Example 65. The reaction wascarried out at reactive hydrogen pressure of 140 kg/cm², reactiontemperature of 420° C. and liquid space velocity of 0.5 Hr⁻¹. Theanalysis of the treated oil showed the following results. Sulfur: 0.31%;Nitrogen: 2,100 ppm; n-heptane-insoluble matter: 0.3%; Vanadium: 2 ppm;and Nickel: 3 ppm.

EXAMPLE 68

A copper and molybdenum on sepiolite-catalyst was prepared in the sameway as in Example 65.

A sepiolite of Spanish product was crushed to the particle size of 1-2mm in diameter and impregnated for a whole day and night in the aqueoussolution containing 0.1 mol/l of magnesium nitrate, followed bysufficient washing with warm water. The treated sepiolite wasimpregnated in the aqueous solution containing 0.02 mol/l of coppernitrate, and rinsed with warm water and then with 5% ammonia water,followed by drying at 120° C. for 2 hours. To the dried sepiolite, wereadded 3% (based on anhydrous alumina) of an aluminium hydrooxide solcontaining 16% of alumina, 25% of attapulgite clay of the U.S. productand 200% of water, followed by wet milling for about 10 hours. Anaqueous ammonium solution of ammonium paramolybdate was then addedthereto and the mixture was sufficiently kneaded, followed by repeatingdrying (at 60° C.) and water spray to adjust the water content thereofto 210%. The moist mixture was molded into cylindrical pellets 1.7 mm indiameter, which was then dried for about a week and calcined at 500° C.for two hours. Thus a copper and molybdenum on sepiolite-catalyst wasobtained. The analysis of the resultant catalyst showed that 2.4% of CuOand 6.4% of MoO₃ were contained therein. The physical properties of thecatalyst measured in the same way as in Example 65 are shown in Table16.

                  TABLE 16                                                        ______________________________________                                        Properties of copper and molybdenum on sepiolite-catalyst                     ______________________________________                                        specific surface area (BET method)                                                                     210 m.sup.2 /g                                       specific surface area (mercury                                                porosimeter method, >30 A)                                                                             107 m.sup.2 /g                                       pore volume (mercury porosi-                                                  meter method, >30 A)     0.74 cc/g                                            pore distribution (mercury                                                    porosimeter method)                                                            30-220 A                0.13 cc/g                                            200-600 A                0.35 cc/g                                            >600 A                   0.26 cc/g                                            crushing strength (radial direction)                                                                   2.2-4.7 kg                                           ______________________________________                                    

Example 67 was repeated to carry out hydrotreating by employing thiscatalyst. The analysis of the treated oil 50 hours after starting thereaction showed the following results. Sulfur: 0.28%; Nitrogen: 2,200ppm; Vanadium: ≦2 ppm; and Nickel: ≦2 ppm.

EXAMPLE 69

A cerium and molybdenum on sepiolite-catalyst was prepared substantiallyin the same way as in Example 68. Crushed sepiolite of Spanish productwas impregnated with stirring in the aqueous solution containing 0.01mol/l of nitric acid and 0.1 mol/l of magnesium nitrate for 5 hours. Thetreated sepiolite was further impregnated in the aqueous solutioncontaining 0.1 mol/l of cerium nitrate for 5 hours to obtain a cerium onsepiolite-material. After the cerium on sepiolite-material wassufficiently washed with warm water, thereto were added, on the basis ofsepiolite, 5% (as anhydrous alumina) of aluminium hydroxide solcontaining 16% of alumina, 25% of bauxite containing 1.8% of TiO₂ and5.1% of Fe₂ O₃, and about 150% of water, followed by subjecting themixture to wet milling for 10 hours. An aqueous ammonium solution ofammonium paramolybdate was added to the ground mixture and thensufficiently kneaded, followed by adjusting the water content thereof to125%. The moist mixture was molded into cylindrical pellets 1.0 mm indiameter, which were air-dried for about one week and then calcined at650° C. for 2 hours. Thus, a cerium and molybdenum on sepiolite-catalystwas obtained. The analysis of the catalyst showed that 1.2% of Ce₂ O₃and 3.1% of MoO₃ were contained therein. The physical properties of thecatalyst were measured to be 146 m² /g in specific surface area (mercuryporosimeter method, diameter ≦30 A) and 0.57 cc/g in pore volume.

Example 67 was repeated to carry out hydrotreating by employing thiscatalyst. The treated oil 50 hours after starting the reaction contained0.45% of sulfur and ≦2 ppm of vanadium.

EXAMPLES 70-72

A hydrogenation catalyst for treating hydrocarbons was prepared from asepiolite of Spanish product. The crushed sepiolite having particlesizes of 1 to 2 mm in diameter was ground to 50 mesh pass, and water wasadded thereto followed by sufficient kneading by a kneader. In thecourse of the kneading, 5.0% (as anhydrous alumina) of aluminiumhydroxide sol containing 20% of alumina was added thereto and themixture was further kneaded to mix it up. By spraying water onto thekneaded mixture, it was homogeneously moistened to adjust the watercontent thereof to 200% and then molded into cylindrical pellets 1.0 mmin diameter by an extruder. The molded pellets were air-dried at roomtemperature for about a whole day and night and further dried at 120° C.for 3 hours. The resultant molded sepiolite product which had beencalcined at 500° C. for 1 hour had a pore volume (mercury porosimetermethod, >30 A) of 0.92 cc/g and a specific surface area (BET method bymeans of N₂ adsorption) of 171 m² /g.

The molded sepiolite product dried at 120° C. was impregnated in 5 timesby volume of an aqueous acidic solution containing 0.1 mol/l of cobaltnitrate, copper nitrate or lanthanum nitrate for about two days andnights and taken out, followed by washing it sufficiently with warmwater at 45° to 50° C. Incidentally, it was observed that magnesium wasdissolved in the acidic aqueous solution. The washing with warm waterwas repeated until a metal ion such as Co ion was scarcely observed inthe waste washing water. The resultant metal on sepiolite molded productwas baked at 200° C. for about 2 hours, and was further calcined at 500°C. for 1 hour to obtain a calcined product. The measurement of thephysical properties thereof according to mercury porosimeter showed thatit had a pore volume in the range of 0.75-0.80 cc/g and a specificsurface area of 115-120 m² /g (>30 A), irrespective of the kind of themetals supported. The color of Co or Cu on sepiolite molded productscarcely changed when baked at 200° or 500° C. and was substantially thesame as that of a sepiolite molded product which did not support themetal thereon.

Onto the Co, Cu or La on sepiolite molded product, an aqueous solutioncontaining a predetermined amount of ammonium paramolybdate and about 7%of ammonia was sprayed to impregnate it with about 6% (as MoO₃) ofmolybdenum. The impregnated product was dried at 120° C. for about 3hours and then calcined at 500° C. for about 1 hour to obtain a Mo andCo, Cu or La on sepiolite-catalyst.

The physical properties of the resultant catalysts as well as theamounts of the metals supported are shown in Table 17.

                  TABLE 17                                                        ______________________________________                                                                     Refer-                                                          Examples      ence                                                            70*   71      72      Ex.                                      ______________________________________                                        Amount of metals supported                                                    CoO, CuO, La.sub.2 O.sub.3 (%)                                                                 CoO;    CuO;    La.sub.2 O.sub.3 ;                                            1.8     2.3     1.1   0                                      MoO.sub.3 (%)    6.1     5.6     6.2   0                                      specific surface area                                                                          147     134     155   171                                    (BET method) (m.sup.2 /g)                                                     pore volume (>50 A)**(cc/g)                                                                    0.77    0.72    0.76  0.92                                   pore distribution**                                                            30-100 A (cc/g) 0.032   0.030   0.026 0.040                                  100-400 A (cc/g) 0.451   0.455   0.466 0.472                                  >400 A           0.290   0.232   0.270 0.409                                  ______________________________________                                         *carrier without catalytic metal                                              **according to mercury porosimeter method                                

From Table 17, it is shown that the pore volumes of the metals onsepiolite-catalysts obtained according to the present invention aresmaller than that of the sepiolite carrier which was obtained by simplycalcining the sepiolite molded product, but the ratio of decrease inpore volume predominates in large pores more than 400 A in diameter.Incidentally, the pore volume of the starting material sepiolite whichhad been simply calcined at 500° C. for 1 hour was 0.59 cc/g. Therefore,the pore volumes of the metals on sepiolite-catalysts according to thepresent invention are far larger than that of the starting materialsepiolite and the ratio of the large pores in the present catalysts islowered in comparison with that of the simply calcined molded product;thus it is understood that the catalysts of the present invention have avery sharp pore distribution.

By employing each of these catalysts, a topped residual oil containing2.62% of sulfur, 3,600 ppm of nitrogen, 130 ppm of vanadium, 41 ppm ofnickel and 3.0% of asphaltene was subjected to hydrotreating. Reactionwas carried out by using a conventional flow-type high pressure reactorat reaction temperature of 375° C., hydrogen pressure of 140 kg/cm² andliquid space velocity of 0.5 Hr⁻¹. The analysis of the treated oil 100hours after starting the reaction showed the results given in thefollowing Table 18.

                  TABLE 18                                                        ______________________________________                                        Impurities in the                                                             treated oil  Example 70  Example 71                                                                              Example 72                                 ______________________________________                                        sulfur (%)   1.15        1.03      1.38                                       nitrogen (ppm)                                                                             2,800       2,400     3,000                                      vanadium (ppm)                                                                             20          26        21                                         nickel (ppm) 11          9         10                                         asphaltene (%)                                                                             1.6         1.4       1.7                                        ______________________________________                                    

EXAMPLE 73

The same sepiolite as employed in Examples 70-72 was impregnated in theaqueous solution containing 0.1 mol/l of ammonium nitrate for a wholeday and night, and then was well rinsed with warm water. The sepiolitewas subjected to wet milling to obtain fine powder, and then 3% (asalumina) of aluminium nitrate was added thereto followed by sufficientkneading by a kneader. The kneaded mixture was repeatedly dried at 80°C. and sprayed with water to adjust the water content thereof to 120%.The moist mixture was molded into cylindrical pellets 1.0 mm indiameter, which were sufficiently air-dried and then dried at 120° C.The method of Examples 70-72 was repeated to have cobalt and nickelsupported on the dried pellets. The resultant pellets were calcined at500° C. for 1 hour to obtain a catalyst of the present invention. Theproperties of the catalyst are shown in Table 19.

                  TABLE 19                                                        ______________________________________                                        Amount of metals supported                                                                           CuO; 2.0%                                                                     MoO.sub.3 ; 6.3%                                       specific surface area  162 m.sup.2 /g                                         pore volume            0.61 cc/g                                              pore distribution                                                              30-100 A              0.058 cc/g                                             100-400 A              0.503                                                  >400 A                 0.046                                                  ______________________________________                                    

By employing this catalyst, a vacuum gas oil containing 2% of sulfur issubjected to desulfurization at hydrogen pressure of 30 kg/cm², reactiontemperature of 380° C., and liquid space velocity of 1.0 Hr⁻¹. Thesulfur content in the treated oil was decreased to 0.29% about 100 hoursafter starting the reaction.

EXAMPLES 74

A Co and Mo on sepiolite-catalyst was prepared substantially in the sameway as in Example 73. To the sepiolite were added 20% (as anhydride) ofattapulgite of the U.S. product instead of aluminium nitrate, 3% (asalumina) of the same aluminium hydroxide sol as employed in Examples70-72, and 3% of ammonium nitrate, followed by kneading. The kneadedmixture was moistened to adjust its water content to 125% and moldedinto pellets, which were dried at 200° C. for 1 hour. The method ofExample 70 was repeated to have cobalt and molybdenum supported on thepellets, which were calcined at 500° C. The analysis of the resultantcatalyst showed that 1.6% of CoO and 6.0% of MoO₃ were containedtherein. The catalyst had a specific surface area of 159 m² /g accordingto BET method. Also it had a whole pore volume of 0.68 cc/g and a largepore volume (>400 A) of 0.102 cc/g, according to mercury porosimetermethod.

By employing this catalyst, a solvent-deasphalted oil was subjected tohydrogenation treatment using the same reaction apparatus as used inExamples 70-72. The deasphalted oil containing 2.4% of sulfur, 26 ppm ofvanadium and 12 ppm of nickel was treated at a reaction temperature of380° C., hydrogen pressure of 100 kg/cm², and liquid space velocity of1.0 Hr⁻¹. The analysis of the treated oil 100 hours after starting thereaction showed the decreases in sulfur content to 1.22%, vanadium to 5ppm, and nickel to 4 ppm.

EXAMPLES 75 and 76

To the same crushed sepiolite as employed in Examples 70-72 were addedand 20% (as anhydride) of a bauxite containing 2.3% (as TiO₂) oftitanium and 4.9% (as Fe₂ O₃) of iron, followed by wet milling by a ballmill. The ground mixture was subjected to levigation at 50 mesh and then3% (as alumina) of an aluminium, hydroxide sol was added thereto withsufficient kneading. The kneaded mixture was calcined at 500° C. untilthe pore volume thereof reached 0.82 cc/g, dried at 80° C., andhomogeneously moisted to adjust the water content thereof to 120%. Theresultant moist mixture was molded into cylindrical pellets 1.5 mm indiameter, which were sufficiently air-dried and then baked at 300° C.for 2 hours. The calcined pellets were impregnated in the aqueoussolution containing 0.02 mol/l of nickel sulfate for about a whole dayand night and then rinsed sufficiently with warm water. The resultantnickel-sepiolite-pellets were baked at 300° C. for 2 hours, and then anaqueous ammonium solution (containing 5% of ammonia) of a predeterminedamount of vanadium oxalate or ammonium paratungstate was sprayed on thepellets to have vanadium or tungsten supported thereon. The sprayedpellets were calcined at 650° C. for 2 hours to prepared a Ni and V onsepiolite- or Ni and W on sepiolite-catalyst. The physical propertiesand the amounts of the metals supported on these catalysts are shown inTable 20.

                  TABLE 20                                                        ______________________________________                                                         Example 75                                                                             Example 76                                          ______________________________________                                        amount of metals supported                                                                       (Ni,V)     (Ni,W)                                          NiO                1.2%       1.3%                                            V.sub.2 O.sub.5 or WO.sub.3                                                                      4.7%       3.1%                                            specific surface area                                                                            155 m.sup.2 /g                                                                           140 m.sup.2 /g                                  (BET method)                                                                  pore volume (>30 A)                                                                              0.61 cc/g  0.66 cc/g                                       pore distribution                                                              30-100 A          0.058 cc/g 0.062 cc/g                                      100-400 A          0.305 cc/g 0.343 cc/g                                      >400 A             0.246 cc/g 0.259 cc/g                                      ______________________________________                                    

By employing each of these catalysts, hydrotreating was carried out byusing the same residual oil and the same apparatus as in Examples 70-72at hydrogen pressure of 140 kg/cm², reaction temperature of 420° C. andliquid space velocity of 2.0 Hr⁻¹. The analysis of the treated oilshowed the results given in Table 21.

                  TABLE 21                                                        ______________________________________                                        Impurities in the                                                             treated oil     Example 75                                                                              Example 76                                          ______________________________________                                        sulfur (%)      1.48      1.21                                                vanadium (ppm)  22        22                                                  nickel (ppm)    11        15                                                  asphaltene (%)  1.3       0.9                                                 ______________________________________                                    

EXAMPLE 77

To the sepiolite which had been ground to fine powder as in Examples70-72 were added, on the basis of 1 kg of anhydrous sepiolite, 1 l. ofthe aqueous solution containing 0.1 mol/l of nitric acid and 5% (asalumina) of an aluminium hydroxide sol containing 20% of anhydrousalumina, followed by sufficient kneading by a kneader. In the course ofthe kneading, the samples of the kneaded mixture were molded by anextruder and calcined at 500° C. to test the pore distribution and porevolume of the calcined pellets according to mercury porosimeter method.The kneading was discontinued after large pores more than 400 A indiameter were scarcely observed in the pore distribution of the moldedtest pellets. Then, the kneaded mixture was homogeneously moistened byrepeating water spray and drying at 80° C. to adjust the water contentthereof to 130%.

The moist mixture was molded into cylindrical pellets 1.0 mm indiameter, which were sufficiently air-dried and baked at 200° C. for 3hours. The baked pellets were impregnated in the aqueous solutioncontaining 0.1 mol/l of ammonium chloride for about two days and nightsand then washed sufficiently with pure water. The rinsed pellets werethen impregnated in the aqueous solution containing 0.1 mol/l of coppernitrate for about two days and nights and then rinsed sufficiently withpure water. The treated pellets were dried at 120° C. and then calcinedat 500° C. for two hours to obtain a copper on sepiolite-catalyst. Theproperties of the catalyst are shown in Table 22.

                  TABLE 22                                                        ______________________________________                                        amount of the metal supported                                                                         CuO 2.8%                                              specific surface area   175 m.sup.2 /g                                        pore volume (>30 A)     0.48 cc/g                                             pore distribution                                                              30-100 A               0.027 cc/g                                            100-400 A               0.42 cc/g                                             >400 A                  0.031 cc/g                                            ______________________________________                                    

By employing this catalyst, the same topped residual oil as used inExamples 70-72 was subjected to hydrotreating under the same conditionsas in Examples 75 and 76. The treated oil 100 hours after starting thereaction contained the following impurities.

sulfur: 2.16%

vanadium: 36 ppm

nickel: 25 ppm

asphaltene: 1.8%

While the invention has been particularly shown and described withreference to the embodiments thereof, it will be understood that theforegoing and other changes can be made without departing from thespirit and scope of the invention.

What is claimed is: .[.1. A hydrodemetallization catalyst comprising an effective amountof a catalyst metal component supported on a sepiolite carrier, the catalyst metal being selected from the group consisting of Mo, W and V..]. .[.2. The hydrodemetallization catalyst of claim 1 wherein the catalyst metal is Mo..]. .[.3. A hydrodemetallization catalyst comprising an effective amount of catalyst metal components supported on a sepiolite carrier, the catalyst metal being(1) at least one member selected from the group consisting of Co., Ni, Fe, Cu and lanthanides and (2) at least one member selected from the group consisting of Mo, W and V..]. .[.4. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) comprises at least 0.1 wt. % based on the weight of the catalyst and the catalyst metal (2) comprises at least 0.5 wt. % based on the weight of the catalyst..]. .[.5. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Cu and the catalyst metal (2) is Mo..]. .[.6. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and the catalyst metal (2) is Mo..]. .[.7. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and Ni and the catalyst metal (2) is Mo..]. .[.8. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Ni and the catalyst metal (2) is Mo..]. .[.9. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Cu and the catalyst metal (2) is V..]. .[.10. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and the catalyst metal (2) is V..]. .[.11. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and Ni and the catalyst metal (2) is V..]. .[.12. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Ni and the catalyst metal (2) is V..].
 13. A sepiolite carrier prepared according to a process comprising:(a) grinding sepiolite to a fine powder, 50% or more by weight of which has a particle size of 100-mesh or finer; (b) adding water to the sepiolite obtained in (a) to adjust the water content thereof to about 20 to about 350% by weight; (c) kneading the resulting mixture in (b), and subsequently (d) air-drying or heat-treating the resulting mixture in (c) at a temperature lower than about 1000° C. .[.14. A hydrodemetallization catalyst comprising an effective amount of one or more catalyst metal components supported on sepiolite, the catalyst metal being selected from the group consisting of the metals of the IIb group and the transition metals of the Periodic Table, and wherein said catalyst is prepared according to a process comprising the steps of: (a) grinding sepiolite to a fine powder, 50% or more by weight of which has a particle size of 100-mesh or finer; (b) adding water to the ground sepiolite to adjust the water content thereof to about 20 to about 350% by weight; (c) kneading the resulting mixture; (d) air-drying or heat-treating the moist kneaded sepiolite at a temperature lower than about 1000° C.; and (e) supporting one or more of said catalyst metal components on the sepiolite, the sequence of steps being (a), (b), (c), (d), and (e) or (e), (a), (b), (c) and (d)..]. .[.15. The hydrodemetallization catalyst of claim 14, wherein in step (e) the sepiolite is contacted with an aqueous acidic solution containing ions of one or more metals selected from the group consisting of the metals of Ib, IIb, IIIa and iron groups of the Periodic Table..]. .[.16. The hydrodemetallization catalyst of claim 14, wherein the aqueous acidic solution has a pH of less than or equal to 7 and wherein said one or more metals are selected from the group consisting of Co, Ni, Fe, Cu and lanthanides..]. .[.17. The hydrodemetallization catalyst of claim 14, wherein the catalyst metal is selected from the group consisting of Cu and the metals of the Va, VIa and iron groups of the Periodic Table..]. .[.18. The hydrodemetallization catalyst of claim 17, wherein the catalyst metal is selected from Mo, W and V..]. .[.19. The hydrodemetallization catalyst of claim 14, wherein step (e) comprises a two-stage treatment consisting essentially of a first step of contacting the sepiolite with an acidic aqueous solution containing ions of one or more metals selected from the group consisting of the metals of the Ib, IIb, IIIa and iron groups of the Periodic Table, and a second step of contacting the resulting sepiolite with a basic aqueous solution containing ions of one or more metals selected from the group consisting of Cu and the metals of the Va, VIa and iron groups of the Periodic Table..]. .[.20. The hydrodemetallization catalyst of claim 19, wherein the aqueous acidic solution has a pH of less than or equal to 7 and wherein said one or more metals are selected from the group consisting of Co, Ni, Fe, Cu and lanthanides..]. .[.21. The hydrodemetallization catalyst of claim 19, wherein in said second step an aqueous ammonia and/or amine solution containing ions of one or more metals selected from Mo, W and V is employed..]. .[.22. The hydrodemetallization catalyst of claim 19, wherein said acid aqueous solution has a pH of less than or equal to 7 and contains ions of one or more metals selected from Co, Ni, Fe, Cu and lanthanides; and wherein said basic aqueous solution is an aqueous ammonia and/or amine solution containing ions of one or more metals selected from Mo, W and V..]. .[.23. The hydrodemetallization catalyst of claim 19, wherein the sepiolite treated in the first step is rinsed with a rinsing liquid before the treated sepiolite is subjected to the second-step treatment..]. .[.24. The hydrodemetallization catalyst of claim 23, wherein the rinsing liquid is water, a basic aqueous solution, or an acidic aqueous solution..]. .[.25. The hydrodemetallization catalyst of claim 14, wherein the sequence of steps is (a), (b), (c), (d) and (e) and the sepiolite is molded after step (d) and before step (e) or after step (e)..]. .[.26. The hydrodemetallization catalyst of claim 25, wherein one or more additives are added to the sepiolite in step (b) or step (c) to enhance the molding properties and molded part strength; said additives being selected from the group consisting of aluminium hydroxide sol, alumina silica sol, silica sol, bauxite, kaoline, montmorillonite, allophane, bentonite, attapulgite, higher alcohols, esters of higher alcohols, ethers of higher alcohols, urea, starch, sucrose and organic molding auxiliaries..]. .[.27. The hydrodemetallization catalyst of claim 26, wherein before or in step (c) the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite..]. .[.28. The hydrodemetallization catalyst of claim 14, wherein the sepiolite is pretreated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite..]. .[.29. The hydrodemetallization catalyst of claim 16, wherein the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite..]. .[.30. The hydrodemetallization catalyst of claim 17, wherein the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite..]. .[.31. The hydrodemetallization catalyst of claim 19, wherein the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite..].
 32. The sepiolite carrier of claim 13, wherein one or more additives are added to the sepiolite in step (b) or step (c) so as to enhance its molding properties and molded part strength; said additives being selected from the group consisting of aluminium hydroxide sol, alumina silica sol, silica sol, bauxite, kaoline, montmorillonite, allophane, bentonite, attapulgite higher alcohols, esters of higher alcohols, ethers of higher alcohols, urea, starch, sucrose and organic molding auxiliaries.
 33. The sepiolite carrier of claim 32, wherein before or in step (c), the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite. .[.34. The hydrodemetallization catalyst of any of claims 27, 28, 29, 30 or 31, wherein said inorganic acids are selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and carbonic acid; the organic acids are selected from formic acid, oxalic acid, acetic acid and tartaric acid; the ammonium salts are selected from ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium carbonate, ammonium oxalate, ammonium acetate and ammonium tartarate and the salts of ammonium derivatives are selected from trimethylamine hydrochloride and aniline hydrochloride..].
 35. The sepiolite carrier of claim 33 wherein said inorganic acids are selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and carbonic acid; the organic acids are selected from formic acid, oxalic acid, acetic acid and tartaric acid; the ammonium salts are selected from ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium carbonate, ammonium oxalate, ammonium acetate and ammonium tartarate and the salts of ammonium derivatives are selected from trimethylamine hydrochloride and aniline hydrochloride. 